Multilayer polymeric membrane

ABSTRACT

Provided is a novel continuous single-step method of manufacturing a multilayer sorbent polymeric membrane having superior productivity, properties and performance. At least one layer of the polymeric membrane comprises sorbent materials and a plurality of interconnecting pores. The method includes: (a) coextruding layer-forming compositions to form a multilayer coextrudate; (b) casting the coextrudate into a film; (c) extracting the film with an extractant; and (d) removing the extractant from the extracted film to form the multilayer sorbent polymeric membrane. The sorbent membrane of this disclosure can find a wide range of applications for use in filtration, separation and purification of gases and fluids, CO 2  and volatile capture, structural support, vehicle emission control, energy harvesting and storage, electrolyte batteries, device, protection, permeation, packaging, printing, and etc.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.15/143,663, filed May 2, 2016, now granted U.S. Pat. No. 9,694,344, thedisclosure of which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This invention pertains to a novel method, and more specifically to acontinuous single-step method, for making a multilayer sorbent polymericmembrane. This invention pertains further to a multilayer sorbentpolymeric membrane manufactured by the method of this disclosure, and toan article, membrane, filter, module, device, packaging and printingmaterials, and process comprising the membrane of this disclosure.

BACKGROUND OF THE INVENTION

Flat-film polymeric membranes can be manufactured by the method ofthermally induced phase separation (TIPS) or nonsolvent-induced phaseinversion (NIPI). The membranes that result are either isotropic oranisotropic, depending on conditions and processes employed for theirmanufacture. Isotropic membranes are uniform throughout in compositionand structure, and typically a monolayer film produced by the TIPSprocess. Anisotropic membranes, on the other hand, are asymmetric andproduced often by the NIPI process. These asymmetric membranes mayconsist of a layered structure, e.g., a thin dense layer supported by athick porous nonwoven substrate. In particular, flat-film polymericmembranes, which are filled with a large quantity of particulates, canfind a wide range of applications for use in filtration, separation andpurification of gases and fluids, CO₂ and volatile capture, vehicleemission control, energy harvesting and storage, electrolyte batteries,device, support, protection, permeation, packaging, printing, and etc.However, the filled membranes often suffer from poor productivity andperformance, due to complexities of their manufacture involving multiplecomponents and processes.

U.S. Pat. Nos. 4,342,811 and 4,550,123 disclose a porous polypropylene(PP) fiber and film for use as protective clothing. The PP membranescontain 10 to 50 wt. % active carbons. U.S. Pat. Nos. 4,833,172 and8,388,878 disclose a method for producing a porous ultrahigh molecularweight polyethylene (UHMWPE) film for breathable and printingapplications. The UHMWPE film contains 65 to 90 wt. % SiO₂. U.S. Pat.No. 5,964,221 discloses a CO₂ absorbent device, which comprises a porousUHMWPE sheet containing 96 to 99.6 wt. % Ca(OH)₂. These prior artmembranes all are monolithic and symmetric in both structure andcomposition, composed either of a polymeric matrix of relatively lowmolecular weight (MW) or an extremely high content of inorganicparticles. As a result, the membranes are often too low in strength orproductivity for a commercially useful product. Moreover, the processedmembranes yet retain a significant fraction of residual solvents,thereby greatly decreasing the performance of the particulate inclusionstherein.

U.S. Pat. Nos. 4,877,679 and 5,032,450 disclose a multilayer absorbentpolymeric membrane, produced by a discrete multistep process, i.e.,laminating and/or coating one or more polymeric layers onto preformedmicroporous substrates. The preformed substrates are monolayer instructure and contain 50 to 90 wt. % SiO₂. Again, these membranesdisclosed are low in productivity due to their complex manufacturingprocesses. The membranes also lack strong adhesion between layers, eventhough it may be improved to an extent via surface treatment, adhesives,ultrasound, heat and pressure techniques, and the like. However, anyadditional process lowers productivity further, and alters orcontaminates the interface that adversely affects properties of theresulting laminate. Yet, despite such efforts, the disclosed laminatescan hardly develop sufficient adhesion when the joint consists largelyof foreign inclusions. U.S. Pat. No. 6,893,483 discloses a two-layeradsorbent membrane, prepared by merely winding low and high densitysubstrates alternately.

The prior art sorbent membranes, in general, suffer from a range ofdrawbacks, due to the nature of the structure and process. It istherefore highly desirable to provide a new method that can improvesignificantly both productivity and performance of flat-film sorbentpolymeric membranes.

SUMMARY OF THE INVENTION

This disclosure relates to a method for producing a novel multilayersorbent polymeric membrane comprising at least one layer comprisingsorbent materials of about 5 to about 100 wt. % and a plurality ofinterconnecting pores. The method includes: (a) coextrudinglayer-forming compositions comprising a matrix polymer through afilm-forming die to form a multilayer coextrudate, wherein at least oneof the layer-forming compositions further comprising the sorbentmaterials and a diluent; (b) cooling the multilayer coextrudate on acast roll to form a multilayer film; (c) extracting the diluent from themultilayer film with an extractant; and (d) removing the extractant fromthe extracted film to form the multilayer sorbent polymeric membrane,wherein the matrix polymer is a film-forming thermoplastic polymerselected from the group of petroleum-based polymers, bio-based polymers,biodegradable polymers and combinations thereof; wherein the sorbentmaterials present in the at least one layer retain their initialsorbability and/or their initial porosity (R_(SBT)) of about 50 to about100%; wherein the at least one layer has a porosity (ϕ_(P)) of about 5%to about 85%; and wherein the multilayer sorbent polymeric membrane isasymmetric.

In one embodiment, the matrix polymer comprises at least one nonpolarpolymer. In some embodiments, the sorbent materials are porous,characterized by an average particle size of about 100 μm or less, anaverage pore volume of about 3.5 cc/g or less, and an averageBrunauer-Emmett-Teller (BET) surface area of about 5,000 m²/g or less.In other embodiments, the diluent is selected from a renewable oil,characterized by an iodine value of about 100 g I₂/100 g or lower, anoleic content of about 50% or higher, an oxidation stability index (OSI)of about 10 hours or greater, or any combination thereof. In certainembodiments, the multilayer sorbent polymeric membrane consists of up toabout 100 layers.

It is therefore an object of the present invention to provide a novelcontinuous single-step method for manufacturing a multilayer sorbentpolymeric membrane of a wide range of materials, compositions andstructures; the membrane providing superior productivity, superiorproperties and superior performance.

It is another object of the present invention to provide an easy andeconomic method of producing a sorbent polymeric membrane havingsuperior sorption kinetics and capacity; excellent permselectivitytowards CO₂, gases, organic volatiles and fluids, and water; exceptionalmechanical strength; and little or no pressure drop of gases or fluidsflowing across the membrane.

It is yet another object of the present invention to provide a novelsorbent polymeric membrane made according to the method of thisdisclosure.

Further objects of the present invention include: i) to provide a methodof producing an asymmetric and/or bio-based polymeric membrane; ii) toprovide a method of recovering substantially all the initial sorbabilityand/or porosity of sorbent materials present in a membrane; iii) toprovide a method of producing superior adhesion between layers of amultilayer membrane; iv) to provide a method of manufacturing a sorbentmembrane having excellent wettability towards nonpolar and/or polarsubstances; v) to provide a novel sorbent membrane for use as aseparator for electrolyte batteries or energy storage devices; and vi)to provide a novel sorbent membrane for use as a support of anasymmetric NIPI membrane.

BRIEF DESCRIPTION OF THE DRAWING

FIGS. 1a, 1b and 1c illustrate a schematic side view respectively of atwo-layer membrane, a three-layer membrane and a five-layer membrane,according to some embodiments of the present disclosure.

FIG. 2 is a micrograph of scanning electron microscope (SEM) taken at amagnification of 2,000× for a typical surface of a multilayer sorbentmembrane of the present disclosure.

FIG. 3 is a schematic illustration of a continuous single-stepmultilayer coextrusion film process in accordance with some embodimentsof the present disclosure.

FIG. 4 is a graph of % recovery (R_(SBT)) of the initial porosity forthe sorbent materials present in the Example membranes as a function ofa pore size in the range of 5 to 320 Å.

FIG. 5 is a graph of peel strength (σ_(P)) for the membranes of Examples19-22.

DETAILED DESCRIPTION OF THE INVENTION

Multilayer polymeric films are known in the art and manufacturedtypically by coextruding multiple polymeric melts through a film-formingdie, as disclosed in great detail in U.S. Pat. Nos. 7,713,636,8,142,893, 8,557,919 and 8,906,510. However, as outlined hitherto, themanufacture of multilayer sorbent flat-film polymeric membranes of anopen pore structure is currently limited to discrete multistepprocesses, i.e., combinations of TIPS, NIPI, nonwoven, coating,lamination, and etc. Therefore, a continuous single-step flat-filmprocess of the present invention for producing a multilayer sorbentpolymeric membrane is surprising and novel, which provides immensebenefits over the prior art process. This invention significantlyimproves the efficiency of the manufacturing process, while providinggreat versatility in design of porous membrane products. The inventionenables an easy and economic production of multilayer sorbent polymericmembranes of a wide variety of materials, compositions and structures,which are otherwise impossible or very difficult to manufacture by priorart techniques into commercially useful products.

In the simplest case, the invention can produce a stable monolayermembrane of superior productivity, superior sorbability and superiorstrength, by extruding the at least one of the layer-formingcompositions comprising a matrix polymer, sorbent materials and adiluent. The membrane may consist up to about 100% of various sorbentmaterials at different compositions. In a still simple case, theinvention can produce an asymmetric two-layer membrane of superiorsorbability and superior permselectivity over CO₂, gases, organicvolatiles and fluids, and water, by coextruding a highly functional skinlayer on a side of a sorbent core layer composed of the at least one ofthe layer-forming compositions.

The invention can produce a membrane consisting of up to about 100layers, in which each layer may provide, separately or in combination,various advantageous functions, e.g., such as absorption, adsorption,regenerability, permeation, selectivity, permselectivity, separation,support, wettability, conductivity, adhesion, sealability, printability,protection, barrier, dissipation, compliance, transition, storage, andthe like. The membrane can be oriented to significantly further improveproperties and performance, while lowering materials cost by thinningthe gauge. It is of great surprise that the multilayer membrane of thisdisclosure has superior strength, superior performance, no delaminationof layers, little or no residual solvents, and restores substantiallyall the pristine properties, such as sorbability, porosity and activity,of the sorbent materials inclusions. This is a remarkable improvementover the prior art product.

Various specific embodiments, versions and examples of the invention aredescribed, including preferred embodiments and definitions that areadopted herein for purposes of understanding the claimed invention.While the following detailed description gives specific preferredembodiments, those skilled in the art will appreciate that theseembodiments are exemplary only and that the invention can be practicedin other ways.

As used herein, the singular terms “a”, “an” and “the” include pluralreferents, unless specified otherwise. Likewise, the plural term“multilayer” as used herein includes a singular referent comprising amonolithic or monolayer structure, unless specified otherwise.

As used herein, the term “micropore” refers to a pore with a size ≤2 nm,the term “mesopore” refers to a pore with a size between 2 and 50 nm,and the term “macropore” refers to a pore with a size ≥50 nm. Unlessspecified otherwise, the term “porous” as used herein refers tomicroporous, mesoporous, macroporous and combinations thereof.

As used herein, the term “sheet” is interchangeable with film. Unlessspecified otherwise, the term “film” as used herein is interchangeablewith “membrane” and also refers to a thinner sheet or a precursormembrane.

As used herein, unless specified otherwise, the term “polymer” includeshomopolymers and copolymers, linear and branched, nonpolar and polar,hydrophobic and hydrophilic, and nonporous and porous polymers.

As used herein, unless specified otherwise, the term “copolymer” refersto a polymer formed by polymerization of at least two differentmonomers, comprising random, alternating, block, and graft copolymers.

As used herein, unless specified otherwise, the term “sorbability”refers to a sorption ability of a sorbent material.

As used herein, the term “a particle size” or “size” refers to adiameter for spherically shaped particles and to a thickness for fibers,whiskers, wires, platelets, and the like.

As used herein, unless specified otherwise, the term “immiscible” refersto the property of a material, which when blended with others, does notform in all proportions a homogeneous single-phase solution on amolecular level.

Layer-Forming Compositions

A multilayer polymeric membrane of the present invention is made fromlayer-forming compositions comprising a matrix polymer, wherein at leastone of the layer forming compositions further comprises sorbentmaterials and a diluent. The matrix polymer is to bind together thesorbent materials within. The sorbent materials are to provide desirablefunctions to the membrane. The diluent is to dissolve the polymer duringmanufacture; and then, to be extracted out of the film leaving behind aplurality of interconnecting pores. The layer-forming compositions maydiffer to each other in components, depending on desired properties andapplications of the resultant membrane.

The at least one of the layer-forming compositions may comprise: i) amatrix polymer of about 0.1 to about 70 wt. %, preferably about 0.5 toabout 60 wt. % and more preferably about 1 to about 50 wt. %; ii)sorbent materials of about 5 to about 90 wt. %, preferably about 10 toabout 85 wt. % and more preferably about 15 to about 80 wt. %; iii) adiluent of about 5 to about 90 wt. %, preferably about 10 to about 85wt. % and more preferably about 15 to about 80 wt. %; and iv)optionally, an additive of up to about 15 wt. %.

In a preferred embodiment, the at least one of the layer-formingcompositions, upon removing the diluent, contains the sorbent materialsof about 5 to about 100 wt. %. The diluent-removed at least one of thelayer-forming compositions may contain the sorbent materials of ≥about10 wt. %, preferably ≥about 20 wt. %, more preferably ≥about 30 wt. %,more preferably ≥about 40 wt. %, more preferably ≥about 50 wt. %, morepreferably ≥about 60 wt. %, more preferably ≥about 70 wt. %, morepreferably ≥about 80 wt. %, more preferably ≥about 90 wt. % and evenmore preferably about 100 wt. %.

The multilayer membrane can be produced from a wide range of feedstockmaterials comprising petroleum-based materials, bio-based materials,biodegradable materials and combinations thereof. In some embodiments,the feedstock materials are petroleum-based materials. In otherembodiments, the feedstock materials are selected from bio-basedmaterials and their mixtures of petroleum-based materials.

Matrix Polymers

The matrix polymer of this disclosure is a film-forming thermoplasticpolymer selected from the group of petroleum-based polymers, bio-basedpolymers, biodegradable polymers and combinations thereof. A wide rangeof thermoplastics, including any membrane-forming polymer known in theart, can be conveniently used as the matrix. In one embodiment, thefilm-forming thermoplastic polymer is nonpolar, polar, sorbent or anycombination thereof. A nonpolar-polar combination may improvewettability and sorbability of the membrane towards selective species.In a preferred embodiment, the film-forming thermoplastic polymer has ahigh or ultrahigh molecular weight.

The polymer may have a weight average molecular weight (Mw) of about1×10⁴ to about 2×10⁷ g/mol, preferably about 5×10⁴ to about 2×10⁷ g/moland more preferably about 1×10⁵ to about 2×10⁷ g/mol. The Mw can bemeasured with gel permeation chromatography (GPC) according to ASTM D6474 for polyolefin (PO), ASTM D 5296 for polystyrene (PS) andpolyester, or the like. Although not particularly restricted, thepolymer may have a polydispersity index (MWD), i.e., a molecular weightdistribution defined as Mw/Mn, of about 1 to about 100, preferably about1 to about 60, more preferably about 1 to about 30, and more preferablyabout 1 to about 15. The Mn represents a number average molecularweight.

The matrix polymer may have a unimodal or multimodal MWD. A multimodalMWD polymer may comprise one or more components, and preferably lessthan about 5 components, of the same polymer, a polymer of the samefamily, a miscible polymer, a copolymer, or combinations thereof. Eachof the component polymers may differ from each other in molecular weight(MW); or may have a unimodal, bimodal, or multimodal MWD. A preferredmultimodal polymer may consist of the same polymers of different MWs.The multimodal MWD may be characterized by one or more peaks orinflection points in GPC, resulting respectively from the components ofa low molecular weight (LMW), a high molecular weight (HMW), or anultrahigh molecular weight (UHMW). The multimodal MWD polymer can beprepared by extruder or reactor blending or by any suitable means, asdisclosed in, e.g., U.S. Pat. Nos. 4,461,873, 7,163,906, 8,101,687,8,148,470, and 9,637,573.

In some embodiments, the matrix polymer has a unimodal or multimodal MWDcomprising at least one of: a) an UHMW component of 0 to about 70 wt. %having an Mw greater than about 1,000,000 g/mole; b) a HMW component ofabout 30 to 100 wt. % having an Mw of about 10,000 to about 1,000,000g/mole; or c) a LMW component of 0 to about 70 wt. % having a Mw lessthan about 10,000 g/mole. In certain embodiments, the multimodal polymercomprises at least one HMW component in the amount of greater than about10, 30, 50, 60, 70, 80, or 90 wt. %; or in the range of about 20 to 100wt. %, preferably about 30 to 100, about 40 to 100, about 50 to 100,about 60 to 100, and about 70 to 100 wt. %. In certain embodiments, themultimodal polymer comprises at least one UHMW component less than about80, 70, 60, 50, 40, or 30 wt. %; or in the range of about 0.01 to about80 wt. %, preferably about 0.5 to 70, about 1 to 60, about 1 to 50,about 1 to 40, and about 1 to 30 wt. %.

In some embodiments, the matrix polymer is polyolefin (PO) or polyketone(PK) characterized by: a) an Mw of about 1,000 to about 100,000,000g/mole and b) a unimodal or multimodal MWD comprising at least one of:i) an UHMW component having an Mw greater than about 1,000,000 g/mole inthe amount of 0 to about 70 wt. %; preferably 0 to about 60, 0 to about50, 0 to about 40, 0 to about 30, and 0 to about 20 wt. %; ii) a HMWcomponent having an Mw of about 100,000 to about 1,000,000 g/mole in theamount of about 30 to 100 wt. %, preferably about 40 to 100, about 50 to100, about 60 to 100, and about 70 to 100 wt. %; and iii) a LMWcomponent having an Mw less than about 100,000 g/mole and preferably inthe range of about 1,000 to about 100,000 g/mole, in the amount of 0 toabout 70 wt. %, preferably 0 to about 60, 0 to about 50, 0 to about 40,0 to about 30, and 0 to about 20 wt. %.

The nonpolar polymers may include polyolefin (PO), fluoropolymers (FLPs)comprising polytetrafluoroethylene (PTFE), polystyrene (PS) comprisingisotactic PS (iPS) and syndiotactic PS (sPS), hydrophobic polymers,copolymers thereof, derivatives thereof and combinations thereof. The POpolymer may be produced by Ziegler-Natta catalysts, metallocenecatalysts or any other suitable means, as described in U.S. Pat. Nos.7,713,636 and 8,142,893.

Non-limiting examples of the PO polymer include polyethylene (PE),polypropylene (PP), poly(4-methyl-1-pentene) (PMP), polybutene-1 (PB-1),polyisobutylenes (PIB), thermoplastic elastomers (TPEs) thereof,copolymers thereof, modifications thereof, and combinations thereof. ThePE comprises ultrahigh molecular weight polyethylene (UHMWPE), highdensity polyethylene (HDPE), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),branched low density polyethylene (BLDPE), very low density polyethylene(VLDPE), ultralow density polyethylene (ULDPE), and the like. The PPcomprises ultrahigh molecular weight polypropylene (UHMWPP), isotacticpolypropylene (iPP), syndiotactic polypropylene (sPP), (β-nucleatedpolypropylene (β-PP), β-nucleated ultrahigh molecular weightpolypropylene (β-UHMWPP), high-crystalline polypropylene (HCPP), highmelt-strength polypropylene (HMS-PP), mini-random PP (mr-PP), and thelike. The β-PP and β-UHMWPP may comprise a β-nucleating agent, asdescribed in U.S. Pat. No. 6,828,019.

Non-limiting examples of the polar polymers include polyester, such aspolyethylene terephthalate (PET), polytrimethylene terephthalate (PTT),polybutylene terephthalate (PBT), polyethylene naphthalate (PEN),polybutylene naphthalate (PBN), polylactic acid (PLA), polyethylenefuranoate (PEF), polybutylene furanoate (PBF), polyhydroxyalkanoate(PHA), polycaprolactone (PCL), polycyclohexylenedimethyleneterephthalate (PCT), and polycarbonate (PC); polyamide (PA), such asamorphous polyamides, crystalline polyamides, PA6, PA11, PA12, PA46,PA410, PA66, PA610, PA612, PA1010, PA1012, PA MXD6, PA6T, PAST, PA10T,PA6T/DT (D: 2-methyl pentamethylene diamine), PA6I/6T, andpolyphthalamide (PPA); polyhydroxyether (PHE), such as polyhydroxylamino ether, polyhydroxyl amide ether and polyhydroxyl ether ofbisphenol A; cellulose and cellulose derivatives, such as celluloseacetates (CA), cellulose acetate propionates (CAP), cellulose acetatebutyrates (CAB), carboxymethyl celluloses, cellulose nitrates and ethylcelluloses; polyphenylene oxide (PPhO); acrylic polymers (PAcs), such aspolyacrylic acid (PAA), polyacrylonitrile (PAN) and polyvinyl acetate(PVA); fluoropolymers (FLPs), such as polyvinylidene fluoride (PVDF),poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP),poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PTFE-c-PFPVE),polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (PVF)polyethylenechlorotrifluoroethylene (ECTFE), copolymers oftetrafluoroethylene and ethylene (ETFE), perfluorinatedethylene-propylene copolymer (FEP), andtetrafluoroethylene-perfluorovinyl ether copolymer (PFA);poly(p-phenylene sulfide) (PPS); polyimide (PI); polyetherimide (PEI);polyketone (PK); polyether ether ketone (PEEK); polysulfone (PSU);polyethersulfone (PES); polyvinyl chloride (PVC); polyether, such aspolyethylene oxide (PEO), polypropylene oxide (PPO) and polyoxymethylene(POM); polyvinyl alcohol (PVOH); ethylene vinyl alcohol copolymer(EVOH); polysiloxane such as polydimethylsiloxane (PDMS); ionomersthereof, such as neutralized poly(ethylene-co-acrylic acid), sulfonatedperfluorocarbon, acrylic and fluorinated ionomers, andlithium/sodium/zinc ionomers; thermoplastic elastomers (TPEs) thereof,such as poly(ester-b-amide), poly(ether-b-ester) andpoly(ether-b-amide); copolymers thereof; derivatives thereof; blendsthereof with polyolefin; and mixtures thereof.

Polyketone (PK) of this disclosure is a linear alternating copolymer ofcarbon monoxide (CO) and one or more olefins comprising: a copolymer ofCO and ethylene; a terpolymer of CO, ethylene and a second olefin of atleast 3 carbon atoms; or combinations thereof, as disclosed in, e.g.,U.S. Pat. Nos. 3,694,412, 3,835,123, 4,880,903, 5,073,327, 5,229,343,and 5,229,445. The second olefin may comprise: i) aliphatic, such asα-olefins of propylene, 1-butene, isobutylene, 1-hexene or 1-decene; ii)arylaliphatic, such as styrene or ring-alkylated styrenes; or iii)combinations thereof. The PK contains substantially one CO molecule pereach molecule of ethylenically unsaturated hydrocarbon. A preferred PKis a copolymer, a terpolymer, or mixtures thereof, represented by aformula below:

wherein m is an integer greater than 1; n is an integer greater than 0;and the second olefin is propylene in the amount of 0.1 to 10 mole %,preferably 0.2 to 7 mole %, and more preferably 0.3 to 5 mole %.

A preferred petroleum-based polymer comprises PE, UHMWPE, HDPE, ULDPE,PP, iPP, HCPP, HMS-PP, UHMWPP, β-PP, β-UHMWPP, sPS, iPS, PAcs,polyester, PC, PA, PK, PEEK, cellulose, PPhO, FLPs, PVDF, PPS, PI, PSU,PES, PVC, ionomers thereof, TPEs thereof, copolymers thereof,derivatives thereof, or combinations thereof.

A preferred bio-based or biodegradable polymer comprises PO, such as PE,UHMWPE, HDPE, ULDPE, PP, UHMWPP, iPP, HCPP, β-PP and β-UHMWPP; PK;polyester, such as PTT, PLA, PEF, PBF, PC, PHAs, polyhydroxybutyrate(PHB), polybutylene adipate-co-terephthalate (PBAT), polycaprolactone(PCL) and poly(ether-b-ester); PA, such as PA11, PA12, PA410, PA610,PA612, PA1010, PA1012, PPA, amorphous PA and poly(ether-b-amide)(PEBAX); cellulose and cellulose derivatives, such as CA, CAP, CAB,carboxymethyl celluloses, cellulose nitrates and ethyl celluloses;polysaccharides; thermoplastic starches (TPSs); copolymers thereof;derivatives thereof; or combinations thereof.

A preferred sorbent polymer comprises polar polymers, polyacrylates(PAcs), super absorbent polymers (SAPs), PAN, porous polymers,hydrophilic polymers, PA, polysaccharides, cellulose, copolymersthereof, derivatives thereof, or combinations thereof.

Coating Polymers

Optionally, the membrane may be coated at least once with at least oneprimer and/or at least one coating polymer. Non-limiting examples of thecoating polymers include chitosan and cellulose derivatives, polyamide(PA), poly(ether-b-amide) (PEBAX), poly(ether-b-ester), polyethyleneimine, polydimethylsiloxane (PDMS), polyvinylamine (PVAm),polyhydroxyethers (PHEs), polymers with intrinsic microporosity (PIMs),polydicyclopentadiene (PDCPD), polyphenylene oxide (PPhO), polyvinylalcohol (PVOH), polyacrylic acid (PAA), polyurethane (PU), polyurea(PUA), polyamide imide (PAI), polyphosphazene (PPz), polyaliphaticterpene (PAT), poly(l-trimethylsilyl-1-propyne) (PTMSP), polyvinyl ether(PVE), polydopamine (PDA), epoxy and alkyd resins, copolymers thereof,derivatives thereof and combinations thereof. A preferred coating iswater-borne and/or crosslinkable.

Sorbent Materials

The sorbent materials may comprise absorbents, adsorbents orcombinations thereof. The materials may effectively separate, remove orstore substances, such as element, ion, molecule, moisture, vapor, gas,liquid, solid, particle, metal, impurity, contaminant and the likepresent in solid, liquid and/or gas streams. Properties of the sorbentmaterials, such as sorption kinetics and capacity, permselectivity,compatibility, regenerability, etc., may vary depending on theircomposition, size, morphology, surface chemistry and etc. The sorbentmaterials may promote reaction as catalyst.

The sorbent materials may be divided into two groups, i.e., sorbentpolymers and sorbent fillers, depending on their role and morphology inthe membrane. The materials can form a matrix phase or act as fillers toform a disperse or co-continuous phase. The materials may assume a widerange of characteristics, i.e., natural or synthesized, porous orsubstantially nonporous, inorganic or organic, crystalline or amorphous,nano- or micron-sized, hydrophilic or hydrophobic, surface modified,doped and/or coated, or any combination thereof. The materials mayassume a variety of forms, such as platelet, particle, granule, bead,sphere, pellet, fiber, flake, wire, whisker, tube and the like.

In one embodiment, the sorbent materials are sorbent polymers that forma matrix phase. Preferably, a sorbent matrix polymer is stable andstretchable at elevated film processing conditions. The sorbent matrixpolymer may preferably include porous polymers. In other embodiments,the sorbent materials are sorbent fillers. The fillers may have a bulkdensity σ_(B)≤about 3.5 g/cc, an average particle size D₅₀≤about 200 μm,an average aspect ratio, i.e., a ratio of length (L) to thickness (t),γ_(A) about ≤2,000, an average pore volume ϕ_(S)≤about 6.0 cc/g, and anaverage Brunauer-Emmett-Teller (BET) surface area A_(BET)≤about 7,000m²/g.

The σ_(B) may be about 0.001 to about 0.01 g/cc, about 0.01 to about 0.1g/cc, about 0.1 to about 1.0 g/cc, about 1.0 to about 2.0 g/cc, or about2.0 to about 3.5 g/cc. The γ_(A) may be about 0.01 to about 10, about 10to about 100, about 100 to about 1,000, or about 1,000 to about 2,000.The D₅₀ may be about 0.1 nm to about 100 nm, about 100 nm to about 500nm, about 500 nm to about 1,000 nm, about 1 μm to about 50 μm, about 50μm to about 100 μm, or about 100 μm to about 200 μm. The ϕ_(S) may befrom about 0.001 to about 0.1 cc/g, about 0.1 to about 0.5 cc/g, about0.5 to about 1.0 cc/g, about 1.0 to about 1.5 cc/g, about 1.5 to about2.0 cc/g, about 2.0 to about 2.5 cc/g, about 2.5 to about 3.5 cc/g,about 3.5 to about 4.0 cc/g, about 4.0 to about 5.0 g/cc, or about 5.0to about 6.0 g/cc. The A_(BET) may be about 0.001 to about 1 m²/g, about1 to about 50 m²/g, about 50 to about 100 m²/g, about 100 to about 1,000m²/g, about 1,000 to about 2,000 m²/g, about 2,000 to about 3,000 m²/g,about 3,000 to about 4,000 m²/g, about 4,000 to about 5,000 m²/g, orabout 5,000 to about 7,000 m²/g.

In some embodiments, the sorbent fillers are porous, characterized by aD₅₀ of about 1 nm to about 100 μm, a ϕ_(S) of about 0.1 to about 3.5cc/g, an A_(BET) of about 0.1 to about 5,000 m²/g, or any combinationthereof. The fillers may have a broad size distribution, a large ϕ_(S),a large A_(BET), or combinations thereof. The fillers may have a hollowcore-porous shell nanostructure with a varying core-to-shell diameterratio. In certain embodiments, the sorbent fillers are substantiallynonporous, characterized by a ϕ_(S)≤about 0.5 cc/g and an A_(BET)≤about500 m²/g. The fillers may sorb or soak a diluent of about 10 wt. % orless. In a preferred embodiment, the sorbent fillers are nanosized witha D₅₀ of about 0.1 nm to about 1,000 nm.

Non-limiting examples of the inorganic sorbent materials include metaloxides and hydroxides, metalloid oxides and hydroxides, siliceousmaterials, limestone, CaCO₃, Li₂CO₃, K₂CO₃, clay, zeolites, zeotypes,xerogels, aerogels and combinations thereof. The inorganic sorbents maybe used in a hydrated or anhydrous state. The metal and metalloidcompounds may include Li₂O, CaO, MgO, MnO, ZnO, NiO, CuO, Ag₂O, TiO₂,ZrO₂, SbO₂, Al₂O₃, AlOx (1≤x≤3), Fe₃O₄, γ-AlO(OH) (Boehmite), NaOH,LiOH, KOH, Ca(OH)₂, derivatives thereof and combinations thereof. Thesiliceous materials may comprise silica and silicates, including fumedand precipitated silica; SiOx (1≤x≤3); colloidal silica; organosilica;ethoxysilane; silica gel; boro-silicate porous glass; aerogel; silicananotube; mesoporous silicates, such as MCM-41, MCM-48, SBA-1, SBA-15,SBA-16, NFM-1, FDU-1, FDU-12, AMS-6 and AMS-8; phyllosilicates, such assmectite, palygorskite, montmorillonite, hectorite, saponite,halloysite, sepiolite, tuperssuatsiaite, yofortierite, kalifersite,falcondoite, loughlinite and organosilicate; derivatives thereof; orcombinations thereof.

The zeolites and zeotypes may include zeolite A, such as 4A and 5A;zeolite D; zeolite L; zeolite P; zeolite X, such as 10X and 13X; zeoliteY; zeolite β; ZSM; ETS-4 and 10; zorite; silicoalumino phosphates(SAPO); aluminophosphate (AlPO₄); analcime; chabazite; clinoptilolite;erionite; ferrierite; heulandite; laumonitte; mordenite; mesolite;scolecite; stilbite; derivatives thereof; or combinations thereof.

Non-limiting examples of the organic sorbent materials includecarbonaceous materials, organic-inorganic hybrids, porous polymers,sorbent polymers and mixtures thereof. The carbonaceous materials maycomprise activated carbon, carbon black, carbon molecular sieve, carbonfiber, carbide-derived carbon, fullerene, carbon nanotube, graphene,graphene oxide, graphite, carbon coke, mesoporous carbon, polyacene ormixtures thereof. The organic-inorganic hybrids may comprisemetal-organic frameworks (MOF), such as zeolitic imidazolate frameworks(ZIFs), Zn₄O(1,4-benzenedicarboxylate)₃,Zr₆O₄(OH)₄(1,4-benzenedicarboxylate)₆, Al(OH)(1,4-benzenedicarboxylate),Cu₃(1,3,5-benzenetriscarboxylate)₂,Cu₂(3,3′,5,5′-biphenyltetracarboxylic acid),Cu₂(PF₆)(NO₃)(4,4′-bipyridine)₄.2PF₆.32H₂O; Cu(1,4-benzenedicarboxylate)or combinations thereof.

The porous polymers may comprise hyper-crosslinked polymers (HCPs), suchas crosslinked polystyrene (PS) and crosslinked polyethylenimine;covalent organic frameworks (COFs); polymers of intrinsic microporosity(PIMs); conjugated polymers, such as polyacetylene (PAC), polyphenylenevinylene (PPV), polyaniline (PANI), polysilane, polytriazine (PTA) andpolyphenylene butadiynylene (PPB); fluorinated polymers; polynorbornane(PNB); polyarylene ethynylene; poly(l-trimethylsilyl-1-propyne) (PTMSP);copolymers thereof; or combinations thereof. A preferred porous polymeris melt or solvent processable at elevated temperatures and highlystretchable under the orientation conditions.

Preferred sorbent materials comprise sorbent polymers, Li₂O, CaO, ZnO,TiO₂, ZrO₂, SbO₂, Al₂O₃, AlOx (1≤x≤3), LiOH, Ca(OH)₂, SiO₂, SiOx(1≤x≤3), organosilica, mesoporous silicates, montmorillonite,organosilicates, zeolite A, zeolite X, ZSM, ETS, zorite, aerogels,activated carbon, carbon molecular sieve, carbon fiber, carbon nanotube,graphene, graphene oxide, graphite, mesocarbon, zeolitic imidazolateframeworks (ZIFs), Cu-BTC MOFs, hyper-crosslinked polymers (HCPs),covalent organic frameworks (COFs), polymers of intrinsic microporosity(PIMs), conjugated polymers, poly(l-trimethylsilyl-1-propyne) (PTMSP),derivatives thereof, or combinations thereof.

Additives and Compatibilizers

An additive and compatibilizer may be present in one or more layers ofthe membrane, as taught in great detail in U.S. Pat. Nos. 7,713,636 and8,142,893. An effective amount of the materials may vary depending upondesired properties of the membrane. Non-limiting examples of theadditive include catalysts, cavitating agents, nucleating agents,surfactants, humectants, antioxidants, crosslinking agents, anti-foulingagents, moisture barriers and combinations thereof. The catalysts, e.g.,manganese oxide, copper oxide, hopcalite and precious metal, mayaccelerate an oxidation reaction of contaminants. The cavitating andnucleating agents may further control the pore structure of themembrane. The surfactants and humectants may increase wettability of afluid onto the film surface.

Suitable antioxidants may include phenolic and phosphite antioxidants,such as pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate]methane,tris(2,4-di-tert-butylphenyl)phosphite,tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenyldiphosphonite, andcombinations thereof. The antioxidants may be used in an amount of about0.01 to about 5 wt. %, based on the weight of the layer to which it isadded.

A compatibilizer is typically used to promote interfacial adhesionbetween components in blends, layers in structure, or between both. Thematrix polymer may be composed essentially of the compatibilizer.Suitable compatibilizers may include polar-modified nonpolar polymers,nonpolar-modified polar polymers, copolymers, thermoplastic elastomers(TPEs), nanofillers and combinations thereof.

Nucleating Agent

The nucleating agent (NA) of this disclosure is capable of creatingpolymorphs, e.g., α- and β-crystals in PP, or increasing thecrystallization site, rate, amount or temperature (Tcc) of the matrixpolymer upon cooling from the molten state. The Tcc is commonly termed acold crystallization temperature; it is measured by differentialscanning calorimetry (DSC). The NA can be organic or inorganic, beingselected from any nucleator known in the art or made by any convenientmeans. See, e.g., G. Wypych, Handbook of Nucleating Agents, ChemTech,Toronto, 2016. The NA may be added to the matrix polymer at any stageduring synthesis or processing via a dry or master batch blend, or byany known or suitable means. A preferred method is to use the masterbatch.

In one embodiment, one or more matrix polymers of the membrane comprisea NA of about 0.001 to 5, about 5 to 20, about 20 to 40, or about 40 to60 wt. %; or in the range of about 0.001 to about 60 wt. %, preferablyabout 0.01 to about 50 wt. %. In certain embodiments, the matrix polymercomprises an organic NA of about 0.001 to about 5 wt. %, preferablyabout 0.005 to about 3.5 wt. %, and more preferably about 0.01 to about2 wt. %. In one embodiment, a nucleated matrix polymer has ΔTcc greaterabout 0, 1, 2, 3, 4, 5 or 10° C.; or in the range of about 0 to about30, about 0.5 to about 20, or about 1 to about 10° C. The ΔTcc is adifference of Tcc between a nucleated (N) and pristine (P) polymer,i.e., ΔTcc=Tcc (N)−Tcc (P). In certain embodiments, the ΔTcc is negativein the range of about −5 to about 0° C., due presumably without beingbound to any theory to the induction time of certain NAs that createsimultaneously a large amount of crystal nuclei.

Nonlimiting examples of suitable NAs include inorganic and organicparticles; amides; imides; esters of a diol; pigments; nanocrystallinecelluloses (NCCs); alkali waxes; alkaline earth metal salts ofphosphinates, phosphonates, phosphates, sulfinates, sulfonates,sulfates, hydroxides, and aliphatic and aromatic mono- orpolycarboxylates; derivatives thereof; and combinations thereof. Apreferred salt may have cations and anions selected from the groupconsisting of Li, Na, K, Ca, phosphate, sulfate, acetate, propionate,adipate, pimelate, suberate, phthalate, terephthalate, isophthalate,naphthalate, and the like.

In one embodiment, the NA for polar polymers is selected from the groupconsisting of the sorbent materials, glasses, micas, talcs, kaolinites,clays, wollastonites, TiO₂, polyhedral oligomeric silsesquioxane (POSS),NCCs, dibenzylidine sorbitol, carbonates, adipates, Na and Li benzoates,citrates, acetals of sorbitol and xylitiol, ethylene bis-stearamide,disodium bicyclo[2.2.1]heptanedicarboxylate, PEG esters, PEGbis(2-ethylhexanoate), PEG dilaurate, monosodium terephthalates andnaphthalates, trisodium phosphate (Na₃PO₄), alkyl aryl phosphates,cyclic bis-phenol phosphates, sodium acetate (NaOAc), sodium montanate,sodium and calcium stearates, anthraquinones, perylenes, quinacridones,ionomers of ethylene and ester, polar and nonpolar waxes, rapidlycrystallizing or UHMW polymers, liquid crystalline polymers (LCPs),fluoropolymers (FLPs), and combinations thereof. A preferred NAcomprises inorganic nanoparticles, benzoates, monosodium terephthalatesor naphthalates, disodium bicyclo[2.2.1]heptanedicarboxylate, Na₃PO₄,NaOAc, montanates, stearates, ionomers, polybutylene terephthalate(PBT), polybutylene naphthalate (PBN), FLPs, or combinations thereof.

In one embodiment, the NA for PE, the α-crystal of PP or nonpolarpolymers is selected from the group consisting of salts of mono- andpolycarboxylic acids, e.g., sodium benzoate, aluminum tert-butylbenzoate, disodium bicyclo[2,2,1]heptane-2,3-dicarboxylate and calcium1,2-cyclohexanedicarboxylate; dibenzylidene sorbitols and derivatives,e.g., 1,3:2,4-dibenzylidene, methyldibenzylidene, ethyldibenzylidene anddimethyldibenzylidene sorbitols, and1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol; saltsof phosphate diesters, e.g., sodium 2,2′-methylenebis(4,6,-di-tert-butylphenyl)-phosphate and aluminumhydroxy-bis[2,2′-methylene-bis(4,6-di-tert-butylphenyl)-phosphate];benzene trisamides, e.g.,N,N′,N″-tris-tert-butyl-1,3,5-benzenetricarboxamide andN,N′,N″-tris-cyclohexyl-1,3,5-benzenetricarboxamide; vinylalkane andvinylcycloalkane polymers; NCCs; waxes; and combinations thereof.

In one embodiment, the NA for the β-crystal of PP is selected from thegroup consisting of amide compounds, e.g., dicarboxamides andN,N′-dicyclohexyl-2,6-naphthalene dicarboxyamide; alkali and alkalineearth metal salts of mono-, di- and polycarboxylates comprisingpotassium 1,2-hydroxystearate, magnesium benzoate, magnesium phthalate,magnesium succinate, calcium salts of pimelic, suberic, phthalic andterephthalic acids, and calcium salts of N-phthaloyl glycine; esters ofdibasic and tribasic carboxylic acids; tetraoxaspiro compounds, e.g.,3,9-bis[4-(N-cyclohexylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecane;salts of aromatic sulfonate, e.g., sodium benzenesulfonates andnaphthalenesulfonates; pigments, e.g., quinacridones, quinacridones,quinones, dihydroquinacridones and phthalocyanine blues; mixtures ofmagnesium and cyclic phosphorus compounds; nanosized irons and metaloxides; and combinations thereof.

A β-PP of this disclosure refers to a PP, bio- or petroleum-based,comprising an effective amount of β-NAs. In one embodiment, aβ-nucleated layer of the unoriented PP cast sheet comprises a relativeamount (Xβ) of β-crystallinity greater than about 20, 30, 40, 50, or60%; or in the range of about 20 to 100%, preferably about 30 to 100%,more preferably about 40 to 100%, and more preferably about 50 to 100%.The Xβ can be measured with DSC or wide angle X-ray diffraction (WAXS).The β-crystals present in the unoriened sheet undergo a transitionduring orientation into the α-crystals; thus, leaving behind pores butlittle or no β-crystal residues in the oriented film. However, theoriented film may yet retain the β-NAs therewithin, exhibiting aβ-crystallinity when measured with the second DSC heating scan. Theβ-NAs may also be removed substantially all out of the membrane duringthe extraction process. In certain embodiments, the membrane comprisessubstantially no β-NAs and thus, substantially no β-crystallinity.

In a preferred embodiment, the PP matrix comprises about 0.001 to about10, about 0.005 to about 5, or about 0.01 to about 3 wt. % of α- orβ-crystal NAs. A preferred α-NA may include sodium benzoate, disodiumbicyclo[2,2,1]heptane-2,3-dicarboxylate,1,3:2,4-bis-(3,4-dimethyl-benzylidene) sorbitol, sodium2,2′-methylenebis-(4,6-di-tert-butyl-phenyl) phosphate,hydroxybis-(2,4,8,10-tetra-tert-butyl-6-hydroxy-12h-dibenzo-(d,g)(1,3,2)-dioxaphosphocin-oxidato)aluminum,1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol,N,N′,N″-tris-tert-butyl-1,3,5-benzenetricarboxamide, or combinationsthereof. A preferred β-NA may include N,N′-dicyclohexyl-2,6-naphthalenedicarboxyamide, γ-quinacridones, calcium pimelates, calcium suberates,calcium phthalates, calcium salts of,3,9-bis[4-(N-cyclohexylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,calcium dicarboxylates, nanosized salts of dicarboxylic acids, orcombinations thereof.

Diluent

A diluent may also be termed as “process oil”, “solvent” or“plasticizer”. The diluent may be a solid, a liquid, or combinationsthereof. Properties of the diluent, such as chemical structure,polarity, viscosity, boiling point, molecular weight, stability and thelike, have an impact on structure and properties of the resultantmembrane. The diluent may be compatible with the matrix polymer atelevated temperatures, forming a homogeneous solution and then phaseseparating upon cooling around the solidification or melting temperature(Tm) of the matrix polymer. At room conditions, however, the diluent canbe a good, poor or non-solvent for the matrix polymer. The diluent maypreferably be incompatible with the sorbent materials to promoteextraction. A preferred diluent is a liquid, characterized by aviscosity at 40° C. of about 500 mm²/s or less (ASTM D 445) and aboiling point of about 400° C. or lower (ASTM D 7169).

Nonpolar polymers may employ a nonpolar diluent. Examples of thenonpolar diluent may include aliphatic, alicyclic or aromatichydrocarbons, such as nonane, decane, decalin, p-xylene, undecane,dodecane, terpene and the like; mineral oils; mineral oil distillates,such as paraffinic oil, naphthenic oil, aromatic oil and mixturesthereof; waxes; and combinations thereof.

Polar polymers may employ a polar diluent. Non-limiting examples of thepolar diluent include renewable oils; ethers, such as diphenyl ether(DPE), polyphenyl ether (PPE), glymes, polyethylene glycol (PEG) andpolypropylene glycol (PPG); amides, such as N,N-dimethyl-9-decenamide(DMDA), 1-methyl-2-pyrrolidone (NMP), dimethyl acetamide (DMA), dimethylformamide (DMF) and tetramethylurea (TMU); amines such as diethanolamine(DEA); alcohols, such as stearyl, oleyl, decyl and nonyl alcohols andglycerine; esters, comprising: triacetin, terephthalates such asbis(2-ethylhexyl) terephthalate (DOTP), adipates such as dioxtyladipate, phthalates such as dialkyl phthalate (DAP), citrates, such astriethyl citrate and acetyl tributyl citrate (ATBC), organic carbonatesand phosphates, such as triethyl phosphate (TEP), trisbutoxyethylphosphate and trimellitate; ketones, such as benzophenone, cyclohexanoneand methyl nonyl ketone; acids, such as decanoic acid and oleic acid;aldehydes; tetramethylene sulfone (TMS); dimethyl sulfoxide (DMSO);derivatives thereof and combinations thereof.

In a preferred embodiment, the diluent is a renewable oil comprising alipid, selected from the group of vegetable oils, animal oils, fats,waxes and combinations thereof. Non-limiting examples of the renewableoil include soybean oil, corn oil, olive oil, canola oil, rapeseed oil,sunflower oil, castor oil, linseed oil, palm oil, palm kernel oil,coconut oil, safflower oil, peanut oil, cottonseed oil, tall oil, tungoil, babassu oil, hemp oil, fish oil, whale oil, tallow, tallow amine,lard and combinations thereof. Preferred renewable oils comprise coconutoil, palm oil, palm kernel oil, canola oil, olive oil, peanut oil,cottonseed oil, sunflower oil, corn oil, soy bean oil, tallow, lard andcombinations thereof.

In a yet preferred embodiment, the renewable oil has an iodine value(IV) of about 150 g I₂/100 g or lower and preferably about 100 g I₂/100g or lower, measured according to ASTM D 1959 or AOCS Method Cd1d-92; anoxidation stability index (OSI) of about 5 hours or greater, preferablyabout 10 hours or greater and more preferably about 15 hours or greater,measured at 110° C. according to AOCS Method Cd12b-92; and/or an oleiccontent of about 40% or higher and preferably about 50% or higher, basedon the fatty acid content of the oil, measured according to AOCS methodCa5a-40. The preferred renewable oil may be prepared from varioussources, such as genetically modified organisms, modification of regularrenewable oils, renewable resources and combinations thereof. Themethods of modifying regular renewable oils may include hydrogenation,epoxidation, catalytic deoxygenation, pyrolysis, electrolysis,hydrotreatment and combinations thereof.

Nonlimiting examples of the preferred renewable oils include geneticallymodified soybean oils, high oleic soybean oils, hydrogenated soybeanoils, genetically modified vegetable oils, high oleic vegetable oils,hydrogenated vegetable oils, epoxidized vegetable oils, high oleicsunflower oils, palm oil, palm kernel oil, castor oil, coconut oil,babassu oil, olive oil, lard, tallow and combinations thereof.

Extractant

The extractant can be a good solvent for the diluent, a poor solvent forthe polymer and inert to other components of the layer-formingcompositions. The extractant may be a mixture of water soluble andinsoluble solvents to facilitate extraction of polar and nonpolaranalytes. The extractant may have a low boiling point, a low viscosity,a low surface energy, non-flammability and a low toxicity. The boilingpoint may be about 250° C. or lower, preferably about 220° C. or lower,and more preferably about 190° C. or lower. The viscosity may be about0.1 mm²/s or less. The surface tension may be about 100 mN/m at 25° C.or lower, preferably 80 mN/m or lower, and more preferably 75 mN/m orlower. In one embodiment, the extractant has a surface tension of about10 mN/m or lower.

Non-limiting examples of the extractant include subcritical andsupercritical fluids (SCFs) based on CO₂, CHF₃, N₂O, H₂O, methane,ethane, propane, ethylene, propylene, butane, isobutane, dimethyl ether,sulphur hexafluoride, ammonia, fluorocarbon, methanol, ethanol and thelike; liquid CO₂; water; n-propyl bromide (nPB); aqueous alkalines ofNaOH, KOH and the like; ionic liquids; N,N-dimethylformamide (DMF);chlorinated hydrocarbons, such as methylene chloride, chloroform,dichloroethylene, trichloroethylene (TCE), perchloroethylene,dichloroethane and trichloroethane; alcohols, such as methanol, ethanoland isopropanol; ketones, such as acetone, n-methyl-2-pyrrolidone andmethyl ethyl ketone (MEK); ethers, such as diethyl ether,dimethoxyethane, tetrahydrofuran (THF), dioxane, dioxolane andpolyethylene glycol (PEG); esters, such as methyl ester, ethyl acetateand dimethyl carbonate (DMC); 2-methyl tetrahydrofuran (2-MeTHF); methylsiloxane; hydrocarbons, such as pentane, hexane, cyclohexane, heptane,toluene, decane and terpene; halogenated hydrocarbons; halogenatedethers; azeotropes comprising halogenated hydrocarbons, halogenatedethers, hydrofluoroethers and mixtures thereof; derivatives thereof; andcombinations thereof.

In some embodiments, the extractant is a chlorinated hydrocarbonselected from the group of methylene chloride, chloroform,dichloroethylene, trichloroethylene (TCE), perchloroethylene,dichloroethane, trichloroethane and combinations thereof. In otherembodiments, the diluent is a green solvent selected from the group ofdimethyl carbonate (DMC), ethyl acetate, 2-methyl tetrahydrofuran(2-MeTHF), methyl ester, supercritical fluids, derivatives thereof andcombinations thereof. In a preferred embodiment, the diluent issubcritical and supercritical fluids (SCFs) comprising CO₂. For example,a supercritical CO₂ (SC—CO₂) is an excellent solvent for nonpolar orsmall polar molecules owing to its weak polarity. In a yet preferredembodiment, the diluent is a mixture of a SCF and a polar solvent. Thepolar solvent may preferably comprise water, alcohols, ionic liquids,fluorocarbons, siloxanes and combinations thereof. In a yet preferredembodiment, the diluent is the azeotrope.

Layer Structure and Composition

The multilayer membrane of this disclosure may consist of up to about100 layers. Each layer may vary in pore structure and function,depending on desired applications. The at least one layer comprisessorbent materials and a plurality of interconnecting pores, bothdispersed uniformly throughout the polymeric matrix. The membrane mayhave a thickness (t) of about 1 μm to about 5 mm. An unoriented membranecan be thick with a t of about 300 μm to about 5 mm. An orientedmembrane may be thinner with a t of about 1 μm to about 500 μm.Preferably, the membrane is oriented with increasing sorbability withstretching by up to about 15 times, each in MD and/or TD.

The membrane has a lower density than its layer-forming compositions. Ina preferred embodiment, the at least one layer has a porosity (ϕ_(P)) ofabout 5 to about 85%. The membrane may have a porosity (ϕ_(P)) of about1 to about 20%, about 20 to about 35%, about 35 to about 55%, about 55to about 75%, or about 75 to about 90%. The interconnecting pores mayhave an average diameter of about 0.01 nm to about 50 μm, preferablyabout 0.1 nm to about 30 μm, more preferably about 1 nm to about 20 μm,more preferably about 1 nm to about 10 μm and even more preferably about1 nm to about 5 μm.

In a yet preferred embodiment, the at least one layer contains thesorbent materials of about 5 to about 100 wt. %. The at least one layermay contain the sorbent materials of ≥about 10 wt. %, preferably ≥about20 wt. %, more preferably ≥about 30 wt. %, more preferably ≥about 40 wt.%, more preferably ≥about 50 wt. %, more preferably ≥about 60 wt. %,more preferably ≥about 70 wt. %, more preferably ≥about 80 wt. %, morepreferably ≥about 90 wt. % and even more preferably 100 wt. %. Althoughnot particularly restricted, the at least one layer may contain thesorbent materials of about 0.1 to about 5 wt. %. The membrane maycomprise the sorbent materials ≤100 wt. %.

In a yet preferred embodiment, the sorbent materials present in the atleast one layer retain their initial sorbability, porosity, and/oractivity (R_(SBT)) of about 50 to 100%. The at least one layer may havea R_(SBT) of ≥about 40%, preferably ≥about 50%, more preferably ≥about60%, more preferably ≥about 70%, more preferably ≥about 80%, morepreferably ≥about 90% and even more preferably 100%.

FIG. 1a shows an example of a two-layer membrane of this disclosure,consisting of a first layer 11 and a second layer 12 disposed on a sideof the first layer 11. FIG. 1b shows an example of a three-layermembrane, further comprising a third layer 13 disposed on a side of thefirst layer 11 opposite the second layer 12. FIG. 1c shows an example ofa five-layer membrane, further comprising a fourth layer 14 disposed ona side of the second layer 12 and a fifth layer 15 disposed on a side ofthe third layer 13 opposite the fourth layer 14. The membrane mayconsist of four layers, comprising layers 11, 12, 13 and 14. FIG. 2shows a typical surface image of a membrane of this disclosure. Themembrane contains a finely dispersed co-continuous multiphasemorphology, characterized by a fibrous matrix 21, a dispersed filler 22,and an interconnecting pore 23.

The innermost layer 11 is often termed as a core layer. The core layeris to serve as a monolayer membrane or to provide the foundation of themultilayer structure. In one embodiment, the core layer is the at leastone layer and has a thickness (t) of about 10 to about 100% of the totalfilm thickness. The core layer may provide the membrane with a varietyof other advantageous functions. The layer may be permeable and/orconductive to selective species, wettable, adhesive, printable, orsealable. The core layer may support adjacent layers, separatesubstrates, store species, insulate current, or provide barrier againstpermeating molecules.

The intermediate layer, e.g., layer 12 or 13 of the 5-layer membrane, isoften termed as a tie layer. The tie layer is to bond adjacent layerstogether. In one embodiment, the intermediate layer is highly sorptive,porous and connects adhesively two adjacent layers. The layer may have athickness (t) of ≤about 5 μm, ≤about 10 μm, ≤about 50 μm, or about 0.01to about 70% of the total film thickness. The two intermediate layersmay be symmetric. In other embodiments, the intermediate layer comprisesat least one compatibilizer. The intermediate layer may also providetransition between layers, yield elastically, seal defects of theadjacent layers, or dissipate the applied stress.

The outermost layer, e.g., layer 12 or 13 of the 3-layer membrane andlayer 14 or 15 of the 5-layer membrane, is often termed as a skin layer.The skin layer is to provide a desired function to the membrane. The twoskins may be asymmetric. In one embodiment, the skin layer is highlyporous with a porosity (ϕ_(P)) ≥30%. The layer may have a t of ≤about 1nm, ≤about 1 μm, ≤about 10 μm, ≤about 50 μm, ≤about 100 μm, or about0.01 to about 70% of the total film thickness. The layer may be highlypermselective and/or highly sorptive toward permeating species,adhesive, printable, sealable, wettable, or conductive to current andions. The skin layer may also provide a diffusion pathway for or barrieragainst substances to be sorbed, support the core layer, or protect themultilayer structure.

In a preferred embodiment, the membrane consists of at least two layers.The layers may consist of the same materials at different compositions.The layers may differ in component materials. The core layer maycomprise at least one polyolefin polymer. At least one layer maycomprise a polar polymer, a sorbent polymer, a miscible polymer blend,an immiscible polymer blend, a compatibilizer or any combinationthereof. At least one layer may comprise adsorbent materials, absorbentmaterials or combinations thereof. At least one layer may comprisemesoporous sorbents. At least one layer may be substantially nonsorbentand/or substantially nonporous.

Process of Membrane Manufacture

FIG. 3 illustrates an example of a continuous single-step coextrusionfilm process of this invention, comprising: a feeding system 10, acoextrusion process 20, a casting unit 30, an extractor 40, orienters 50and 60, and a dryer 70. The coextrusion process consists of threeextruders 21, i.e., one main and two satellite extruders. A driedmembrane may be calendered or stretched further at least in onedirection 80, wound 90 and then, slit into a desirable dimension. Atleast one unit of the continuous process can run in a batch orsemi-continuous manner. The manufacturing process may further comprisein-line, although not shown in FIG. 3, surface treaters, coaters,laminators, thin film deposition processes and the like, as taught inU.S. Pat. Nos. 7,713,636, 8,142,893 and 8,557,919.

Feeding of Raw Materials: Prior to being fed into extruders 21,hygroscopic raw materials can be dried to a moisture level ≤50 ppm. Theraw materials may be pre-blended in groups or all together, and then fedinto the extruders with feeders 11-13. The raw materials may preferablybe metered into the extruders, each separately and without pre-blending.Solid feedstocks may be metered into the extruders via a main feeder 11,and liquid feedstocks can be pre-heated and then injected downstream viaa second feed 12, a third feeder 13, or both.

Coextrusion: The feedstock materials fed are dissolved at elevatedtemperatures and mixed homogeneously within each extruder. Thehomogeneous melt is then conveyed to a film-forming die 22 through amultilayer feedblock, to form a multilayer coextrudate. Extrusionconditions are set in a way of ensuring a homogeneous mixing of the fedmaterials, while not to cause excessive degradation of any component. Amonolithic or monolayer extrudate can be produced with a single extruderor by coextruding the same composition with multiple extruders. Amultilayer structure is constructed through coextrusion or coextrusionplus in-line coating. The in-line coating may be carried out by anyconvenient method known in the art, such as roll coating, gravurecoating, die coating, extrusion coating and the like. Alternatively, thelayer-forming compositions may be first compounded into masterbatches,which are then re-extruded to form a multilayer coextrudate.

The extruders may be a single or multiple screw extruder having multiplefeed ports downstream along the machine. A twin screw extruder ispreferred, having a length (L) to diameter (D) ratio (L/D) of about 15to about 65 and preferably about 25 to about 55. The twin screws mayrotate in a co- or counter-direction, and preferably have a series ofintense mixing and kneading sections. The coextrusion process may employa tandem extruder, consisting of single and/or twin screw extruders.Preferably, the coextrusion process yields a homogeneously mixed meltwithin a short residence time at a high output rate.

Film Cooling: A coextrudate 23 issuing out of the film-forming die iscast onto a cast roll 32 to form a multilayer sheet 34. The cast rolltemperature is set to be chill, generally ≤60° C., to cool or solidifythe coextrudate. For rapid quenching or coagulation, the casting process30 may employ an air knife, a water bath, a series of rolls, anyadditional cooling means, or combinations thereof. The design of thequenching system may depend on compositions of the coextrudate, processconditions, and target profiles. A sufficiently low roll temperature canproduce an asymmetrically structured film, i.e., a denser roll-side skinthan the opposite air-side skin. A high roll temperature, on the otherhand, may result in a reversed structure, i.e., a denser air-side skinthan the roll-side surface. In a preferred embodiment, the rolltemperature is sufficiently low enough to produce an asymmetric sheet.

The casting process may employ a series of roll stacks, to calender thesheet to a target thickness and/or to emboss a flow channel pattern suchas a rib onto one or both surfaces of the sheet. A calender or embossingstack 35 that consists of a series of rolls may be installed separatelyafter the casting unit 31-33. The cast sheet may be calendered,alternatively or additionally, after extraction 40 or MD orientation 52,or prior to winding 80 at temperatures around or below the crystallinemelting point (Tm) of the matrix polymer. Calendering is to decrease theporosity of the resulting film, while increasing the connectivity anddensity of the disperse phase. The calender rolls are typicallyconfigured to have a gap decreasing with each successive pass.

The flow channel pattern may be embossed along the machine direction(MD) or at any suitable angle to the MD. The pattern can be linearand/or curved. In some embodiments, the pattern is a rib which, when thefilm is stacked or wound together, forms an internal flow channel fromone to the other end of the rolled web. The flow channels may have adepth ≥about 50% of the film thickness and a width to depth ratio ≥0.5.In other embodiments, the film is calendered without any flow pattern.In certain embodiments, the cast sheet is neither calendered norembossed.

Diluent Extraction: The diluent is extracted at temperatures ≤Tm of thematrix polymer, by passing the film around a series of rolls locatedinside a washing 41 and rinsing stage 42 of the extractor 40. Theextractor 40 is filled with an extractant. Any prior art method used fornon-sorbent films may be employed, e.g., evaporation, dipping,countercurrent flow, showering, washing and combinations thereof. Theused extractant may be recycled similarly to those disclosed in U.S.Pat. Nos. 4,648,417 and 5,772,935. In some embodiments, the extractor 40is a countercurrent flow apparatus, comparted into sections into which afresh extractant enters counter to the machine direction (MD). Theextractor 40 is equipped with a washing and rinsing stage that can stripoff the diluent from the film surface. The extracted film, withoutorientation, can be dried and wound into a web.

In a preferred embodiment, the extractor 40 is equipped with anultrasonic extraction unit (USE) comprising a high-power sonicator 43.The sonicator produces an ultrasonic frequency of about 10 kHz to about1 GHz and preferably about 20 kHz to about 20 MHz. The sonic horn 43 mayemploy a piezoelectrically activated ultrasonic transducer, located onthe top area of the extractor 40. In another preferred embodiment, theextractor 40 is a supercritical fluid extractor (SFE) that runs aroundor beyond the supercritical conditions of the extractant. For example, acarbon dioxide (CO₂) extractant may run around or above itssupercritical conditions, i.e., 31.3° C. and 7.38 MPa, in which CO₂ isin a subcritical, supercritical, or liquid state. In a yet preferredembodiment, the extractor 40 is equipped with both USE and SFE andemploys a supercritical CO₂ extractant. In a yet preferred embodiment,the extraction is carried out by a batch or semi-continuous manner thatenables a substantial increase of the film line speed. The batch orsemi-continuous extractor may be equipped with USE, SFE, or both.

Film Stretching: Orientation 50-60 of the film is optional butpreferred. The cast sheet may be stretched at least in one directionbefore or after extraction 40. In one embodiment, the sheet isuniaxially oriented in the machine direction (MD) with a series of rolls51-52 or in the transverse direction (TD) with a tenter frame 60-61. Inanother embodiment, the sheet is biaxially oriented. The cast sheet maybe stretched first in the MD 52 and subsequently in the TD 61. The sheetmay also be stretched simultaneously 60 both in the MD and TD. Theoriented film can be calendered and/or stretched further 80 in one ormore directions. The film is then wound 90 and slit into a desireddimension. In a preferred embodiment, the sheet is simultaneouslybiaxially oriented after the extraction and then further orienteduniaxially in the TD.

The uniaxial orientation in MD or TD can be conducted at a stretch ratio≤about 15 and temperatures between around the glass transitiontemperature (Tg) and around the flow or crystalline melting temperature(Tm) of the matrix polymer. The biaxial conditions are similar to theuniaxial ones. The tenter frame may consist of 5 sections: a preheatingzone, a stretching zone, a cooling zone, an annealing zone, and a dryingzone. The orientation may spread the particle inclusions across theplane of the film, but yet the inclusions retain close proximityensuring desired properties. Preferably, the orientation is to increaseor cause little change in sorbability of the film. The orientation maybe carried out, following the procedures described in U.S. Pat. No.8,142,893. Preferred orientation processes may include a blown process,a double bubble process, a uniaxial roll process, a biaxial tenter frameprocess, and combinations thereof.

Extractant Removal: The extracted film can be dried by passing itthrough a forced air dryer. Although not shown in FIG. 3, the air dryermay be located immediately after the extractor 40. The drying can removesubstantially all residual diluents and extractants. The drying may becarried out, alternatively or additionally, using part 70 of the tenterframe. The drying temperature can be set to around or below Tm of thematrix polymer. For multicomponent systems, the drying temperature maybe determined by the lower Tm of the component polymers or the Tm of themajor component. The dried film, i.e., the membrane, may be re-dried oractivated prior to use.

In some embodiments, the membrane contains substantially no residualdiluents and extractants. The residual diluent may be present in themembrane in an amount of ≤about 3.0 wt. %, preferably ≤about 1.0 wt. %,more preferably ≤about 0.1 wt. %, even more preferably ≤about 0.01 wt.%, and the most preferably ≤about 0.001 wt. %. In other embodiments, themembrane retains about 3 to about 25 wt. % of the residual diluent. Themembrane may contain a residual extractant of ≤about 10 ppm, preferably≤about 1 ppm, more preferably ≤about 0.1 ppm, even more preferably≤about 0.01 ppm, and the most preferably ≤0.001 ppm. The content of theresidual solvent can be determined according to EPA Method 8260 B.

Additional Processes: At least a portion of one or both of the outersurfaces of the membrane may be treated at any stage during manufacture,to provide surfaces with chemical species or high energy forcrosslinking, coating, lamination, printing, deposition and the like.The surface treatment may be carried out according to any method knownin the art, such as corona discharge, plain and polarized flametreatment, plasma treatment, chemical treatment, radiation treatment,and combinations thereof.

At least a portion of one or both outer surfaces of the membrane may becoated once or more with at least one primer and/or at least onepolymer, as described in U.S. Pat. Nos. 3,753,769, 4,058,645, 4,439,493,and 7,713,636. The coating may provide a desired function, such aspermselectivity, absorption, adsorption, separation, permeation,wettability, conductivity, adhesion, sealability, printability,protection, barrier, transition, or combinations thereof. The coatingmay be applied with any convenient manner known in the art, such as rollcoating, gravure coating, die coating, extrusion coating, spraying,dipping, solution casting, deposition and combinations thereof. Theapplied coating may be dried by hot air, radiant heat, or any otherconvenient means. In a preferred embodiment, the film is in-line coatedand the coating is crosslinked during any stage between the casting 30and winding 90 processes.

The coatings may have a thickness of about 0.01 nm to about 20 μm,preferably about 0.1 nm to about 10 μm, and more preferably about 1 nmto about 1 μm. In some embodiments, the coatings have a thickness ofabout 0.1 to about 10 nm. Preferred coatings may comprise one or moresorbent materials of about 0.01 to about 100 wt. %, preferably about 0.1to about 95 wt. % and more preferably about 1 to about 90 wt. %, basedon the weight of the dried coating. In other embodiments, the coatingsconsist essentially of sorbent materials, sorbent polymers, orcombinations thereof. In a preferred embodiment, the coatings comprisenanoscale sorbent materials of about 0.1 nm to about 1,000 nm in size.

EXAMPLES

Membranes of the present invention are further described with referenceto the following non-limiting examples. The properties of the examplesare measured according to the following test methods.

Test Method

Particle Properties: Mastersizer 3000 of Malvern Instrument was used tomeasure an average particle size and a particle size distribution of thesorbent materials. Before and after processing, the adsorbent materialswere characterized with a nitrogen adsorption porosimetry (MicromeriticsASAP 2020) (ASTM D6556) for a pore volume (ϕ_(S)), a pore sizedistribution (PSD) and a Brunauer-Emmett-Teller (BET) surface area(A_(BET)). The gas volume adsorbed at various vapor pressures wasrecorded for the adsorption and desorption steps. Recovery (R_(SBT), %)of the initial porosity for the materials was then calculated:

$R_{SBT} = {\frac{{Measured}\mspace{14mu}{Porosity}\mspace{14mu}{of}\mspace{14mu}{Particles}\mspace{14mu}{in}\mspace{14mu}{the}\mspace{14mu}{Dried}\mspace{14mu}{Membrane}}{{Initial}\mspace{14mu}{Porosity}\mspace{14mu}{of}\mspace{14mu}{Particles}} \times 100}$

For the absorbent materials, the R_(BST) was calculated in a similar wayby weighing the samples, before and after immersing them for 24 hr intowater or hydrocarbon. During the measurement, the wettability of thesamples was also examined with these polar and nonpolar liquids. Ingeneral, the R_(BST) value was correlated proportionally to changes insorbability of the materials.

Thickness (t, μm): The average thickness of the membrane was measured bya caliper and a dial gauge thickness meter at 1 cm interval along the MDand TD of a 10 cm×10 cm specimen. Five measurements on each membranesample were averaged. The dial gauge thickness meter had a resolution ofabout 1 μm with a maximum reading error ≤3 μm. An optical microscopy wasalso used to measure the overall and layer thicknesses of the membranes.

Porosity (ϕ_(P), %): The membrane porosity was measured by measuring thespecimen density: ϕ_(P)=100×(d_(O)−d_(M))/d_(O), wherein d_(M) and d_(O)are respectively the measured and calculated density. The specimendensity was measured by measuring the specimen yield and volume. Yieldis the measure of the specimen coverage per unit weight, measuredaccording to ASTM D-4321. The size and volume of the interconnectingpores were also measured according to the mercury intrusion method.

Tensile Properties: Tensile tests were performed in the MD and TD withan Instron 4400 machine in accordance with ASTM D882. An average of fivemeasurements on each sample was reported.

Shrinkage Ratio (%): The heat shrinkage ratios in the MD and TD weremeasured after exposing the membrane at 105° C. for 8 hours in an oven.An averaged value of three measurements was used.

Air Permeability (N_(G), s/100 cm³/25 μm): The air permeability of themembrane was measured according to ASTM D726. The Gurley number (N_(G))is a time required for a specific amount of air to pass through aspecific area of the specimen under pressure. When the porosity andthickness of the specimen are fixed, the N_(G) is then to measure thetortuosity of a porous structure. A pressure drop (AP) along thecross-flow unit of a spiral wound membrane module was measured using theair of 5.5 MPa and 50° C. The measured AP was scaled from 1 to 5. Thelower the scale, the lower the AP.

Phase Morphology: The micrographic images of scanning electronmicroscopy (SEM) were taken with Jeol JSM 6400. Fresh cross-sectionsurfaces were prepared by freeze fracturing the specimen perpendicularand parallel to MD at −130° C. using liquid nitrogen. The fresh surfaceswere subsequently coated with platinum, and images were then taken at anacceleration voltage of 25 KV. The SEM images were also used to measurethe size, thickness or dimension of the continuous and disperse phases,including particles, aggregates, fibrils, platelets, tubes, and etc.

Peel Strength (σ_(P), g/cm): A 12 μm poly(ethylene terephthalate) (PET)film was laminated onto the skin layer of the membrane specimen with Dow522 A&B adhesive. The coat weight of the adhesive was about 0.84kg/ream. Both sides of the laminated specimen were then supported bytaping with 3M Scotch™ 610 tape. The taped specimen was cut to about2.54 cm wide by about 12.7 cm long along the machine direction. The peelstrength was then measured at the 90° mode at room conditions with anInstron machine (Sintech 1, MTS System Corporation). A delaminatingspecimen generally has σ_(P)≤50 g/cm.

Feedstock Materials

The materials used in Examples and Comparative Examples were allcommercially available products. TABLE 1 lists the physical propertiesof the matrix polymers, such as melt flow index (MFI), intrinsicviscosity (IV, g/dl), weight average molecular weight (Mw), molecularweight distribution (MWD), density (p) and crystalline meltingtemperature (Tm). In case of multi-melting polymers, the listed Tmrepresents the highest crystalline melting point. The polymers werepetro- and bio-based, including ultrahigh molecular weight polyethylene(UPE), high density polyethylene (HDPE), isotactic polypropylene (PP),β-nucleated PP (β-PP), ultrahigh molecular weight PP (UPP), ultrahighmolecular weight β-PP (β-UPP), polyimide 66 (PA66), poly(ethyleneterephthalate) (PET), poly(vinylidene fluoride) (PVDF) with a meltviscosity of 50 kPs at 100 s⁻¹ and 232° C., PVDF copolymer withhexafluoropropylene (PVdF-HFP), and 16/84% ethylene/propylenethermoplastic elastomer (TPE) and its maleated grade (m-TPE). Eachpolyolefin comprised about 0.1 wt. % antioxidant. Unless specifiedotherwise, the matrix polymers were petro-based and the mixtures wereall 70/30 wt. % blends.

TABLE 2 shows the physical properties of the sorbent materials, such asaverage particle size (D₅₀), porosity (ϕ_(S)), BET specific area(A_(BET)) and bulk density (ρ_(B)). The materials used included:powdered activated carbon (PAC), mesoporous PAC (m-PAC), calciumhydroxide Ca(OH)₂, mesoporous silica MCM-41, zeolite 4A, mesoporouszeolite (ZSM-5), carbon nanofiber (CNF), aminosilane-treated zeolite13X, oxidized graphene (GRP), lithium hydroxide (LiOH), metal organicframework of Cu₃(BTC)₂ (HKUST-1), zeolitic imidazole framework of2-methylimidazole zinc salt (ZIF-8), polybenzodioxane (PIM-1) andnanosilica (SiO₂). Both Ca(OH)₂ and LiOH were anhydrous with moisture≤0.5 wt. %. The sorbent mixtures were all 60/40 wt. % blends, unlessspecified otherwise.

The diluents used included nonpolar and polar solvents, i.e., paraffinwax (PW), liquid paraffin (LP), diphenyl ether (DPE), dibutyl phthalate(DBP), and vegetable oil (VTO). The VTO was a genetically modified higholeic soybean oil having an oleic content ≥80% and an oxidationstability index (OSI) ≥60 hours. The extractants were pentane (PTN),hexane (HXN), trichloroethylene (TCE), an azeotrope (AZ) of 70/20/10 wt.% trans-1,2-dichloroethylene/decafluoropentane/heptafluorocyclopentane,dimethyl carbonate (DMC), and supercritical CO₂ fluid (SC—CO₂).

TABLE 1 MFI Mw MWD ρ Tm Polymer (g/10 m) (10⁵ g/m) (Mw/Mn) (g/cc) (° C.)UPE / 30 / 0.94 135 HDPE 0.1 7 5.2 0.96 130 PP 1.5 5 5.5 0.9 160 β-PPUPP / 30 6.5 0.9 165 β-UPP PA66 / 2 / 1.14 250 PET 0.85 (IV) / / 1.27240 PVDF 0.1 / / 1.78 170 PVdF-HFP 0.1 / / 1.78 170 TPE 8   0.7 2.10.862 95 m-TPE

TABLE 2 D₅₀ ϕ_(S) A_(BET) ρ_(B) Sorbent (nm) (cc/g) (m²/g) (g/cc) PAC 12× 10³ 1.5 1450 0.55 m-PAC 12 × 10³ 1.5 1450 0.55 Ca(OH)₂ 13 × 10³ / /0.56 MCM-41 300 1.3 1270 0.35 Zeolite 4A 3.5 × 10³ 0.7 750 0.61 ZSM-5300 0.8 450 0.72 CNF 125  0.15 100 0.06 Zeolite 13X 3.5 × 10³ 0.7 7500.55 GRP 10 2.5 1010 0.51 LiOH 13 × 10³ / / 0.79 HKUST-1 16 × 10³ 1.32100 0.35 ZIF-8 500  0.65 1800 0.33 PIM-1 500 1.1 900 / SiO₂  30 / 500.41Film Processing

The coextrusion film line, shown in FIG. 3, equipped with three twinscrew extruders was used. The main extruder had a screw diameter of 25mm and an L/D of 40. The satellite extruders had a 16 mm screw of 35L/D. The processing conditions were optimized for each composition,according to properties of the feedstock materials. Prior to extrusion,all hydrophilic solid feedstocks were dried for about 5 hrs attemperatures of 50 to 250° C. to moisture level ≤50 ppm. The extrudersran at the range of 150 to 350° C., 100 to 1,000 rpm, and a total outputof 5 to 30 Kg/hr.

Some powder feedstocks were pre-blended with a tumbler mixer. Thecomponents were then metered into the extruder with the main feeder. Thediluent was heated to about 150° C. and injected into the extruderdownstream via the second feed port located prior to the first kneadingsection. Extrudates issuing out of a 6 inch wide film-forming die werequenched into a sheet using a chill roll set to 10 to 100° C. Forselected examples, a rib pattern of an isosceles trapezoid was embossedwith a patterned roll on one surface of the cast sheet. The isoscelestrapezoid had a dimension, based on the sheet thickness, of an upperbase length of 60%, a bottom base length of 125% and a height of 50%.The pattern was aligned in the TD at an interval 200% of the sheetthickness.

The cast sheet was unoriented or oriented at temperatures of 100 to 300°C., and then extracted at temperatures of 30 to 100° C. or under the CO₂supercritical condition. For selected samples, the extraction wasassisted by a high-power sonicator (S) running at 50 kHz. The extractionand/or calendaring were done, respectively prior to or afterorientation. The supercritical fluid extraction (SFE) was also carriedout in a batch mode as follows: i) a 20×20 cm diluent-laden film wasplaced in a 1.5-liter vertical stirred high-pressure vessel, whichsubsequently was charged with 700 ml SC—CO₂ at 50° C. and 10 MPa; andthen ii) the sample was extracted twice, each for 30 min under 20 kHzultrasound; and then dried for 30 min in a hot air oven at 100 to 200°C.

Examples C1-C3 and 1-10

TABLE 3 shows the layer structure, composition, and process conditionsof Comparative Examples C1-C3 and Examples (EX) 1-10. Except for a sodalime Ca(OH)₂ of C2, the sorbent materials used were carbons andzeolites. C1-C3 were prepared according to the conventional methods, amonolayer membrane with a very high and a very low polymer content. Arib pattern was embossed on C2 film. C1 film was stable, splittinginfrequently during processing. However, C2 and C3 films were toobrittle for a continuous operation, along with fractions of the particleinclusions falling out of the matrices. In contrast, EXs 1-10 were amultilayer film, all asymmetric in composition and/or structure. TheExample films contained at least one layer containing a low polymercontent ≤2.5 wt. %, similar to C2 and C3 films. Surprisingly, however,all the Example films were stable with little or no instability andsplits.

EX 1 had a skin layer identical in composition to C3, i.e., a highlysorbent skin, but the core layer had a higher polymer content. EXs 2-3contained a UPE or UPP matrix, with a rib pattern embossed on onesurface. EX 2 was extracted under ultrasound (S). EX 4 was a 3-layerfilm, composed of a UPE/UPP blend and MCM-41. The skin layer had a largeamount 80 wt. % of the incompatible diluent with MCM-41. EXs 5-6 werecomposed of PP blends, oriented biaxially by 3×3; but, their layersdiffered, within ≤8 wt. %, in polymer content. EXs 7-10 had all abio-based polyolefin matrix, unoriented or oriented, which exhibited abetter stability presumably owing to carbon nanofiber (CNF) and β-UPPused in the films. EXs 5-10 employed “green” extractants. EXs 9-10 weremade all with bio-based renewable feedstocks.

TABLE 4 shows the experimental results of the Example membranes, i.e.,composition, thickness (t), recovery (R_(SBT)) of the sorbent porosity,porosity (ϕ_(P)) of the films and film layers, Gurley number (N_(G)) andpressure drop (AP). Equally biaxially stretched membranes had similartensile properties in MD and TD. Although C1 membrane had a low tensilestrength, it was ductile but tended to elongate during processing. Thiswas found due to its high PP content. C2-C3 membranes were substantiallybrittle with a low tensile strength (STR)≤0.1 MPa. Overall, C1-C3membranes were also poor in other properties, such as a high N_(G), alarge AP, and a high shrinkage ratio.

TABLE 3 Composition Polymer Sorbent Diluent P/S/D Orientation EX Layer(P) (S) (D) (wt %) Rib Extract MDX TDX C1 Mono PP PAC PW 58/17/25 X PTN/ / C2 UPE Ca(OH)₂ LP 1/49/50 ◯ HXN / / C3 UPE PAC LP 1/39/60 X TCE / /1 Skin UPE PAC LP 1/39/60 X TCE / / Core 4/36/60 2 Skin UPE PAC LP2/38/60 ◯ TCE/S / / Core UPE/HDPE 4/36/60 3 Skin UPP ZSM-5 DPE 4/36/60 ◯TCE / / Core 2.5/47.5/50 4 Skin UPP/UPE MCM-41 DBP 1/19/80 X TCE/S / /Core 4/36/60 Skin 1/19/80 5 Skin UPP/PP 4A DBP 1.5/27.5/70 X AZ 3 3 Core8/32/60 Skin 1.5/27.5/70 6 Skin UPP/β-PP PAC DBP 2.5/47.5/50 X AZ/S 3 3Core 5/45/50 Skin 2.5/47.5/50 7 Skin UPP 13X/CNF LP 2.5/47.5/50 X DMC // Core 5/45/50 8 Skin β-UPP PAC/CNF LP 2.5/47.5/50 X DMC/S 3 / Core5/45/50 9 Skin UPE 13X/GRP VTO 2.5/47.5/50 X SC—CO₂ 3 3 Core 6/34/60 10Skin UPE/PE PAC/GRP VTO 2.5/47.5/50 X SC—CO₂/S 3 3 Core 6/34/60 Skin2.5/47.5/50

TABLE 4 Membrane Tensile (MD) Porosity (%) Shrinkage P/S STR STN Film MDTD Gurley EX Layer (wt %) t (μm) (MPa) (%) R_(SBT) (ϕ_(P)) (%) (%) (s)ΔP C1 Mono 77/23  500 1.1 12 <10 45 6.1 4.5 153 5 C2 2/98 500 <0.1 <5<10 56 4.3 3.4 121 3 C3 2.5/97.5 500 <0.1 <5 65 56 4.3 3.4 121 4 1 Skin2.5/97.5 200 12.3 17 85 19 1.2 1.2 95 3 Core 10/90  300 17 2 Skin 5/95300 16.5 21 98 18 1.1 1.3 78 1 Core 10/90  500 19 3 Skin 10/90  300 15.319 90 18 <1 <1 83 1 Core 5/95 500 15 4 Skin 5/95 50 19.5 25 99 56 <1 <177 1 Core 10/90  100 10 Skin 5/95 50 57 5 Skin 5/95 50 75.2 42 90 51 <1<1 65 1 Core 20/80  100 15 Skin 5/95 50 52 6 Skin 5/95 50 78.6 33 100 17<1 <1 93 3 Core 15/85  100 15 Skin 5/95 50 19 7 Skin 5/95 50 26.5 18 8618 <1 <1 57 3 Core 10/90  100 8 Skin 5/95 35 92.5 45 100 17 <1 <1 76 3Core 10/90  65 15 9 Skin 5/95 35 87.5 43 92 14 <1 <1 88 3 Core 15/85  6517 10 Skin 5/95 25 85.2 51 100 15 <1 <1 61 3 Core 15/85  50 19 Skin 5/9525 16In contrast, EXs 1-10 membranes all had an asymmetric pore structurealong with superior tensile properties, i.e., stress (STR) at break ≥10MPa and strain (STN) at break ≥15%. The oriented membranes were thint≤100 μm, with significantly further improved tensile strengths. The PPmatrix was found the most stable, producing consistently a uniformlythin gaged membrane. EXs 2-3 membranes were thick t=800 μm, with anembossed rib pattern resulting in a low AP in the cross-flow test.Surprisingly, however, EXs 4-5 membranes, even without ribs, yielded alow AP similar to EXs 2-3. This improvement was presumed owing to theirhighly porous thick skins, providing a flow pathway that effectivelyreplaced the embossed rib pattern, thereby improving productivity of thefilm line.

FIG. 4 shows a plot of % recovery (R_(SBT)) of the sorbent porositypresent in the processed membrane as a function of a pore size in themicro- and mesopore range from 5 to 320 Å. C1 membrane had a lowporosity recovery R_(SBT)≤10%, showing occlusion of substantially allthe sorbent pores by the diluent. Even after a prolonged drying at 130°C. for 24 hrs, yet C1 membrane increased marginally the pore recoveryR_(SBT)≤20%; thus, performing poorly in adsorption. C3 membrane showedan improvement, yet lost most microporosity ≤20 Å of the sorbent pores.It was found due in part to good affinity between PAC and LP, whichtended to prevent the LP extraction out of the PAC pores. On contrary,EXs 1-10 membranes recovered substantially all the porosity R_(SBT)≥85%.Further improvement up to 100% R_(SBT) was made with the solventlesssonicator-assisted supercritical fluid extraction process. The combinedprocess was proven also to be highly efficient, leaving behind noresidual extractants in the membrane.

In short, the Example membranes showed superior sorption kinetics andcapacity far exceeding the Comparative Examples. The membranes were alsosuperior in other properties, i.e., an average pore size ≤500 nm, a filmporosity ϕ_(P)≤30% upon calendering, a Gurley number N_(G)≤100 s/100 cc,a shrinkage ratio ≤1.5%, a low pressure drop ΔP≤3 and excellentwettability towards polar and/or nonpolar fluids.

Examples 11-22

TABLE 5 shows the layer structure, composition, and process conditionsof EXs 11-22. In contrast to C2 film, the Example films were all stablewith little or no processing issues. EXs 11-14 were a monolayer film,having a bio-polymer matrix except for PA66. The cast sheets werequenched rapidly by setting the roll at 10° C. The monolayer films alsodiffered both in composition and process from C2 and the prior arts. TheExample films were variously extracted by combining the novel inventivemethods, i.e., ultrasound, supercritical fluids, incompatibilization,low surface tension extractants, high power and green solvents, etc. EXs11-17 employed sorbents incompatible with diluents. EXs 15-17 were atwo-layer film with a rib pattern. EX 15 incorporated an absorbent inthe core and an adsorbent in the skin. EX 17 was similar in compositionto EX 16, but the film was biaxially oriented without a rib pattern. EXs18-22 contained mesoporous adsorbents, regenerable and superior in CO₂capture and selectivity. Like EX 17, EX 18 had two skin layers high indiluent content. EXs 19-22 were asymmetric, biaxially oriented 3- and5-layer films, wherein the skin and core polymers were immiscible. Thetie layers of EXs 21-22 were symmetric, composed of the maleated TPE.

TABLE 6 shows the measured properties of EXs 11-22 membranes. EXs 11-14were 700 μm thick, excluding the rib dimension, and contained 90 wt. %sorbent fillers. The membrane had a denser skin on the roll side. Also,surprisingly, all the monolayer bio-polymer films were ductile with asuperior tensile strength STR ≥7.3 MPa and without particle fall-out.This was a huge improvement over the prior art products, and presumedowing to the film structure consisting of a nanofibrous matrix, uniformdispersion of components and a very low content of residual low MWspecies. EXs 15-22 further improved tensile properties. EX 22 had theskin layers composed essentially of sorbent materials, i.e., a PA66matrix and sorbent fillers. The membrane was superior in adsorption.Overall, the Example membranes restored substantially all the pristineproperties of the sorbent inclusions, R_(SBT)≥90%, along with thedesirable film properties, i.e., a mean pore size ≤500 nm, a porosityϕ_(P) of 15 to 80% and a low pressure drop ΔP≤3. The oriented membraneswere thin t≤100 μm, with significantly further improved properties.

EXs 11-22 membranes exhibited superior sorption kinetics and capacity,suitable for use as a filter in capturing and/or separating CO₂, gaseousand fluidic contaminants, organic volatiles and solvents, solidparticles, ions, and etc. In particular, the combinations of differentpolymers and different sorbents used in the layers of EXs 13-15 improvedhydration and sorption capacity of the film, while preventing waterpenetration through the matrix. In a CO₂ removal canister test accordingto US NAVY Technical Manual (AD-A160181, 1985), EXs 13-15 showed higherrates and more capacities than EXs 11-12. EXs 17-18, on the other hand,had highly porous skins that lowered AP similarly to the rib-patternedflow channels of EXs 11-16, thus eliminating the embossing process. EX17 membrane was thin, but performed similarly in CO₂ removal to thethick membranes of EXs 15-16.

As shown in FIG. 5, EXs 19-22 underwent no layer delamination along witha superior peel strength σ_(P)≥150 g/cm, which was much higher thanσ_(P)≤50 g/cm of a delaminating control sample (CNTL) disclosed in U.S.Pat. Nos. 7,713,636 and 8,142,893. In general, to prevent laydelamination, a multilayer film is required to have σ_(P)≥about 50 g/cm.EXs 20-21 further increased σ_(P)≥200 g/cm with a m-TPE tie layer. Thisunusually strong interface was of great surprise. Without being bound byany theory, it was presumed owing to both miscible species-inducedinterdiffusion of the dissimilar molecules across the layer boundariesand stress-induced interlocking in-situ of the diffused chains,respectively during the laminar melt and extensional solid flows. EXs18-22 membranes had superior sorbability, which are regenerable and mayeffectively replace conventional sorbent beds or sheets being used in abroad range of filter applications. The Example membranes were alsofound excellent in providing a structural support to anonsolvent-induced phase inversion (NIPI) membrane.

All documents described herein are incorporated by reference, includingany priority documents and/or testing procedures. While various specificembodiments have been illustrated and described, various modificationscan be made without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the disclosure belimited thereby.

TABLE 5 Composition Polymer Sorbent Diluent P/S/D Orientation EX Layer(P) (S) (D) (wt %) Rib Extract MDX TDX 11 Mono UPP/UPE Ca(OH)₂ LP6/53/40 ◯ TCE/S / / 12 β-UPP LiOH LP SC—CO₂/S / / 13 UPP LiOH/13X LPAZ/S / / 14 UPE/PA66 LiOH DBP SC-CO₂/S / / 15 Skin UPE PAC LP 1/49/50 ◯AZ/S / / Core LiOH 5/45/50 16 Skin UPE SiO₂ LP 1/49/50 ◯ TCE/S / / Core5/45/50 17 Skin UPE LiOH LP 1/19/80 X TCE/S 3 3 Core 5/45/50 18 Skin UPPZIF-8 DPE 1/19/80 X SC-CO₂ 3 3 Core MCM-41 8/42/50 Skin ZIF-8 1/19/80 19Skin PET HKUST-1 VTO 5/45/50 X AZ/S 3 3 Core UPP/PET 13X 8/42/50 SkinPET HKUST-1 5/45/50 20 Skin PVDF PIM-1 VTO 4/36/60 X TCE/S 3 3 Core UPEPAC 8/42/50 Skin PVDF PIM-1 4/36/60 21 Skin PVdF-HFP HKUST-1 VTO 2/38/60X SC—CO₂/S 3 3 Tie m-TPE SBA-15 5/45/50 Core UPP 8/42/50 Tie m-TPE5/45/50 Skin PVdF-HFP PIM-1 2/38/60 22 Skin PA66 HKUST-1 VTO 2/38/60 XSC—CO₂/S 3 3 Tie m-TPE m-PAC 5/45/50 Core β-UPP 8/42/50 Tie m-TPE5/45/50 Skin PA66 PIM-1 2/38/60

TABLE 6 Membrane Tensile (MD) Porosity (%) P/S STR STN Film Peel EXLayer (wt %) t (μm) (MPa) (%) R_(SBT) (ϕ_(P)) ΔP (g/cm) 11 Mono 10/90700 8.1 11 93 48 1 / 12 7.5 15 100 57 1 / 13 7.3 11 100 55 1 / 14 8.2 12100 56 1 / 15 Skin  2/95 200 17.5 37 99 59 1 / Core 10/90 500 53 16 Skin 2/98 300 15.5 21 100 57 1 / Core 10/90 400 52 17 Skin  2/98 30 15.5 21100 77 1 / Core 10/90 70 52 18 Skin  5/95 25 42.5 56 95 62 1 / Core16/84 50 22 Skin  5/95 25 64 19 Skin 10/90 20 43.8 51 100 16 3 163 Core16/84 60 15 Skin 10/90 20 18 20 Skin 10/90 20 51.6 57 100 17 3 151 Core16/84 60 19 Skin 10/90 20 18 21 Skin  5/95 10 45.3 42 100 17 3 205 Tie10/90 15 18 Core 16/84 50 19 Tie 10/90 15 17 Skin  5/95 10 16 22 Skin 5/95 10 47.2 45 100 19 3 242 Tie 10/90 15 17 Core 16/84 50 16 Tie 10/9015 16 Skin  5/95 10 18

What is claimed is:
 1. A multilayer sorbent polymeric membranecomprising at least one layer comprising: a matrix polymer, sorbentmaterials of about 100 wt. % or less, and a plurality of interconnectingpores having an average pore size of about 0.1 nm or greater, whereinthe matrix polymer is a film-forming thermoplastic polymer selected fromthe group consisting of petroleum-based polymers, bio-based polymers,biodegradable polymers, and combinations thereof; wherein the sorbentmaterials present in the membrane retain their initial sorbabilityand/or their initial porosity of about 100% or less; and wherein themembrane has a porosity of about 85% or less and a Gurley airpermeability of about 1 sec/100 cc or greater.
 2. The membrane of claim1, wherein the matrix polymer is selected from the petroleum-basedpolymers.
 3. The membrane of claim 1, wherein the matrix polymer isselected from the bio-based polymers and the biodegradable polymers. 4.The membrane of claim 1, wherein at least one matrix polymer has aweight average molecular weight of about 1,000 g/mole to about100,000,000 g/mole, a unimodal or multimodal distribution of themolecular weight, and a molecular weight distribution of about 1 toabout
 100. 5. The membrane of claim 1, wherein at least one matrixpolymer is a nonpolar polymer, a polar polymer, or combinations thereof;wherein the nonpolar polymer comprises: polyolefin (PO), polystyrene(PS), fluoropolymers (FLPs), thermoplastic elastomers (TPEs) thereof,copolymers thereof, derivatives thereof, or combinations thereof; andwherein the polar polymer comprises: polyester, polyamide (PA),fluoropolymers (FLPs), polyether, acrylic polymers (PAcs), polyketone(PK), polyether ether ketone (PEEK), polyphenylene sulfide (PPS),polyimide (PI), polyetherimide (PEI), polybenzimidazole (PBI),polysulfone (PSU), polyethersulfone (PES), polyvinylamine (PVAm),cellulose, polyvinyl alcohol (PVOH), ethylene vinyl alcohol copolymer(EVOH), polysiloxane, thermoplastic starches (TPSs), thermoplasticelastomers (TPEs) thereof, ionomers thereof, copolymers thereof, orcombinations thereof.
 6. The membrane of claim 5, wherein the POcomprises: a) polyethylene (PE) comprising high density PE (HDPE),medium density PE (MDPE), low density PE (LDPE), ultrahigh molecularweight PE (UHMWPE), or combinations thereof; and b) polypropylene (PP)comprising isotactic PP (iPP), high crystalline PP (HCPP), high meltstrength PP (HMS-PP), mini-random PP (mr-PP), ultrahigh molecular weightPP (UHMWPP), β-nucleated PP (β-PP), or combinations thereof; wherein thepolyester comprises: polylactic acid (PLA), polyethylene terephthalate(PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate(PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN),polyethylene furanoate (PEF), polybutylene furanoate (PBF),polycarbonate (PC), polycyclohexylenedimethylene terephthalate (PCT), orcombinations thereof; wherein the PA comprises: PA6, PA11, PA12, PA46,PA66, PA410, PA610, PA612, PA1010, PA1012, PA MXD6, PA6T, PAST, PA10T,polyphthalamide (PPA), PA6T/DT (D: 2-methyl pentamethylene diamine), orcombinations thereof; and wherein the FLPs comprise: polyvinylidenefluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene)(PVdFHFP), poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether)(PTFE-c-PFPVE), poly(vinyl fluoride) (PVF), polychlorotrifluoroethylene(PCTFE), copolymers of tetrafluoroethylene and ethylene (ETFE),polyethylenechlorotrifluoroethylene (ECTFE), perfluorinatedethylenepropylene copolymer (FEP), tetrafluoroethylene-perfluorovinylether copolymer (PFA), or combinations thereof.
 7. The membrane of claim6, wherein the at least one matrix polymer is β-PP comprising aβ-nucleating agent (β-NA) of about 3 wt. % or less, wherein the PPcomprises: iPP, syndiotactic PP (sPP), HCPP, HMS-PP, mr-PP, UHMWPP,copolymers thereof, or combinations thereof; and wherein the β-NAcomprises: N,N′-dicyclohexyl-2,6-naphthalene dicarboxamide,quinacridones, calcium pimelates, calcium suberates, calcium phthalates,calcium salts of3,9-bis[4-(N-cyclohexylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,calcium dicarboxylates, nanosized salts of dicarboxylic acids,derivatives thereof, or combinations thereof.
 8. The membrane of claim1, wherein at least one matrix polymer is a miscible blend, animmiscible blend, a compatibilizer, or combinations thereof.
 9. Themembrane of claim 8, wherein the compatibilizer comprises polar-modifiedpolymers, copolymers, TPEs, nanofillers, or combinations thereof. 10.The membrane of claim 1, wherein the sorbent materials are selected fromthe group consisting of metal and metalloid oxides, metal and metalloidhydroxides, carbonaceous materials, siliceous materials, zeolites,metal-organic frameworks (MOFs), porous polymers, sorbent polymers,derivatives thereof, and combinations thereof.
 11. The membrane of claim10, wherein the sorbent materials are porous, substantially microporous,substantially mesoporous, or substantially macroporous.
 12. The membraneof claim 10, wherein the sorbent materials are sorbent fillerscharacterized by a bulk density of about 3.5 g/cc or less, an averageparticle size of about 100 μm or less, a pore volume of about 3.5 cc/gor less, an aspect ratio of about 2,000 or less, aBrunauer-Emmett-Teller (BET) surface area of about 5,000 m²/g or less,or combinations thereof.
 13. The membrane of claim 12, wherein theaverage particle size is about 1 nm to about 1,000 nm.
 14. The membraneof claim 10, wherein the metal and metalloid compounds comprise: Li₂O,CaO, ZnO, TiO₂, ZrO₂, SiO₂, SiO_(x) (1≤x≤3), Al₂O₃, AlO_(x) (1≤x≤3),LiOH, Ca(OH)₂, γ-AlO(OH), or combinations thereof; wherein thecarbonaceous materials comprise: activated carbons, carbon fibers,carbon nanotubes, graphenes, graphene oxides, mesoporous carbons, carbonmolecular sieves, or combinations thereof; wherein the siliceousmaterials comprise: precipitated silica, fumed silica, organosilica,mesoporous silica, phyllosilicates, organosilicates, aerogels, MCM-41,SBA-15, or combinations thereof; wherein the zeolites comprise: zeoliteA, zeolite X, ZSM, mesoporous zeolites, zeotypes, or combinationsthereof; wherein the metal-organic frameworks (MOFs) comprise: zeoliticimidazolate frameworks (ZIFs), ZIF-8, ZIF-67, HKUST-1, MIL-53, MIL-101,MOF-74, UiO-66, UiO-66-NH₂, derivatives thereof, or combinationsthereof; and wherein the porous or sorbent polymers comprise:hyper-crosslinked polymers (HCPs), covalent organic frameworks (COFs),polymers of intrinsic microporosity (PIMs), conjugated polymers,fluorinated polymers, polytrimethylsilyl propyne (PTMSP),polysaccharides, copolymers thereof, or combinations thereof.
 15. Themembrane of claim 1, wherein the membrane is substantially unoriented;and has a thickness of about 0.1 mm to about 3 mm, a porosity of about5% to about 70%, an average pore size of about 50 μm or less, a Gurleyair permeability of 1,000 sec/100 cc or less, a tensile strength ofabout 0.1 MPa or greater in the machine direction (MD) and/or thetransverse direction (TD), a peel strength of about 30 g/cm or greater,or combinations thereof.
 16. The membrane of claim 15, wherein at leastone portion of at least one outer surface of the unoriented membrane isembossed with a flow channel pattern at any angle along the MD.
 17. Themembrane of claim 1, wherein the membrane is oriented in at least onedirection; and has a thickness of about 1 μm to about 30 μm, a porosityof about 20% to about 85%, an average pore size of about 1 nm to about 1μm, a Gurley air permeability of about 1,000 sec/100 cc or less, acrystalline melting temperature (Tm) of about 125° C. to about 350° C.,a tensile strength of about 10 MPa or greater in the MD and/or the TD, apeel strength of about 30 g/cm or greater, or combinations thereof. 18.The membrane of claim 1, wherein the membrane comprises at least oneouter layer having a porosity characterized by a porosity ratio of about0.01 to about 100 relative to the porosity of an inner layer, an averagepore size characterized by a size ratio of about 0.001 to about 1,000relative to the average pore size of an inner layer, or combinationsthereof.
 19. The membrane of claim 1, wherein at least one portion of atleast one outer surface of the membrane is coated with a layer ofcoating, crosslinking, or both, wherein the coated layer has a thicknessof about 50% or less of the total film thickness; and wherein the coatedlayer comprises at least one component selected from the groupconsisting of metal oxides, SiO₂, SiO_(x) (1≤x≤3), Al₂O₃, AlO_(x)(1≤x≤3), TiO₂, silicates, zeolites, graphenes, MOFs, ZIFs, UiO-66-NH₂,PO, polar modified PO (p-m-PO), olefin block copolymers (OBCs),p-m-OBCs, styrenic block copolymers (SBC), p-m-SBCs, PVOH, PAc, PSU,PVDF, cellulose acetates, chitosans, aromatic PA, PIMs, PTMSP, PI,polyamide imide (PAI), polydopamine, TPEs thereof, ionomers thereof,derivatives thereof, and combinations thereof.
 20. The membrane of claim19, wherein the coated layer is porous having a porosity characterizedby a porosity ratio of about 0.01 to about 100 relative to the porosityof an inner layer, an average pore size characterized by a size ratio ofabout 0.001 to about 1,000 relative to the average pore size of an innerlayer, or combinations thereof.
 21. The membrane of claim 1, wherein themembrane comprises a matrix polymer of about 100 wt. % or less, thesorbent materials of about 0 wt. % to about 99 wt. %, and a nucleatingagent of about 0 wt. % to about 20 wt. %; and consists essentially of:a) a monolayer consisting of the at least one layer; b) two layersconsisting of a first layer and a second layer disposed on a side of thefirst layer; c) three layers consisting of the first layer, the secondlayer, and a third layer disposed on a side of the first layer oppositethe second layer; d) four layers consisting of the first layer, thesecond layer, the third layer, and a fourth layer disposed on a side ofthe second layer; or e) five layers consisting of the first layer, thesecond layer, the third layer, the fourth layer, and a fifth layerdisposed on a side of the third layer opposite the fourth layer.
 22. Themembrane of claim 21, wherein the membrane is the monolayer membrane.23. The membrane of claim 21, wherein the membrane is: a) the two-layermembrane comprising a first layer (A), a second layer (B), and a layerstructure of B/A, wherein the A and B layers differ from each other inmatrix polymer or composition; b) the three-layer membrane comprisingthe first layer (A), the second layer (B), and a layer structure ofB/A/B or A/B/A; c) the four-layer membrane further comprising a fourthlayer (C) with a layer structure of B/C/A/B or A/C/B/A; or d) thefive-layer membrane comprising a layer structure of B/C/A/C/B orA/C/B/C/A.
 24. The membrane of claim 23, wherein the matrix polymer ofthe A layer is PK.
 25. The membrane of claim 23, wherein the matrixpolymer of the A layer is PPS.
 26. The membrane of claim 23, wherein thematrix polymer of the B layer is β-PP.
 27. The membrane of claim 23,wherein the matrix polymers of the A and B layers are PO.
 28. Themembrane of claim 27, wherein: a) the PO of the A layer matrix polymeris HDPE, MDPE, LDPE, UHMWPE, copolymers thereof, or combinationsthereof; and b) the PO of the B layer matrix polymer is PP, β-PP, iPP,HCPP, HMS-PP, mr-PP, UHMWPP, copolymers thereof, or combinationsthereof.
 29. The membrane of claim 23, wherein: a) the matrix polymer ofthe A layer is PO; and b) the matrix polymer of the B layer is PK, PEEK,PPS, polyester, PA, FLPs, ionomers thereof, copolymers thereof, orcombinations thereof.
 30. The membrane of claim 23, wherein the matrixpolymers of the A and B layers are polyester.
 31. The membrane of claim30, wherein: a) the polyester of the A layer matrix polymer is PET, PEN,PEF, copolymers thereof, or combinations thereof; and b) the polyesterof the B layer matrix polymer is PTT, PBT, PBN, PBF, PCT, PC, PLA,copolymers thereof, or combinations thereof.
 32. The membrane of claim23, wherein: a) the matrix polymer of the A layer is polyester; and b)the matrix polymer of the B layer is PK, PEEK, PPS, PA, PI, PEI, PSU,PES, ionomers thereof, copolymers thereof, or combinations thereof. 33.The membrane of claim 23, wherein the matrix polymers of the A and Blayers are PA.
 34. The membrane of claim 33, wherein: a) the PA of the Alayer matrix polymer is PA6T, PAST, PA10T, PPA, PA6T/DT, copolymersthereof, or combinations thereof; and b) the PA of the B layer matrixpolymer is PA6, PA11, PA12, PA46, PA66, PA410, PA610, PA612, PA1010,PA1012, PA MXD6, copolymers thereof, or combinations thereof.
 35. Themembrane of claim 23, wherein: a) the matrix polymer of the A layer isPA; and b) the matrix polymer of the B layer is PK, PEEK, PPS, PI, PEI,PSU, PES, ionomers thereof, copolymers thereof, or combinations thereof.36. The membrane of claim 23, wherein at least one outer layer of themembrane comprises about 99 wt. % or less of the sorbent fillerscomprising: MgO, ZnO, CaO, SiO₂, SiO_(x) (1≤x≤3), TiO₂, ZrO₂, CaCO₃,BaTiO₃, Al₂O₃, AlO_(x) (1≤x≤3), B₂O₃, BaSO₄, Nb₂O₅, Ta₂O₅, silicates,zeolites, graphenes, COFs, MOFs, ZIFs, UiO-66-NH₂, derivatives thereof,or combinations thereof.
 37. The membrane of claim 6, wherein themembrane is made by a method comprising: a) (co)extruding layer-formingcompositions comprising a matrix polymer to form a multilayer(co)extrudate, wherein at least one of the layer-forming compositionsfurther comprising the sorbent materials and a diluent; b) cooling themultilayer (co)extrudate to form a multilayer film; c) extracting thediluent from the multilayer film with an extractant; and d) removing theextractant from the extracted film to form the multilayer sorbentpolymeric membrane.
 38. The membrane of claim 37, wherein the diluent isselected from the group consisting of hydrocarbons, mineral oils,paraffinic oils, naphthenic oils, renewable oils, ethers, amides,amines, alcohols, esters, ketones, acids, aldehydes, sulfones,sulfoxides, derivatives thereof, and combinations thereof.
 39. Themembrane of claim 38, wherein the renewable oils are: a) characterizedby an iodine value of about 150 g I₂/100 g or lower, an oleic content ofabout 50% or higher, an oxidation stability index (OSI) of about 5 hoursor greater, or combinations thereof; or b) selected from the groupconsisting of soybean oils, genetically modified soybean oils, higholeic soybean oils, hydrogenated soybean oils, epoxidized soybean oils,hydroxylated soybean polymerized soybean oils, modified soybean oils,vegetable oils, genetically modified vegetable oils, high oleicvegetable oils, hydrogenated vegetable oils, epoxidized vegetable oils,hydroxylated vegetable oils, polymerized vegetable oils, modifiedvegetable oils, high oleic canola oils, high oleic sunflower oils, palmoil, palm kernel oil, castor oil, coconut oil, olive oil, derivativesthereof, and combinations thereof.
 40. The membrane of claim 39, whereinthe at least one matrix polymer is PO.
 41. The membrane of claim 39,wherein the membrane is a monolayer membrane.
 42. The membrane of claim37, wherein the extraction method further comprises an ultrasonicextraction.
 43. The membrane of claim 37, wherein the extractant isselected from the group consisting of subcritical fluids, supercriticalfluids (SCFs), mixtures of supercritical fluids (SCFs) and polarsolvents, alkyl acetates, organic carbonates, n-propyl bromide (nPB),amides, alcohols, ketones, ethers, esters, hydrocarbons, ionic liquids,halogenated hydrocarbons, halogenated ethers, azeotropes of halogenatedfluids, derivatives thereof, and combinations thereof.
 44. The membraneof claim 43, wherein the subcritical or supercritical fluids comprisecarbon dioxide (CO₂).
 45. An article, cartridge, module, electrolytebattery, or energy storage device comprising the membrane of claim 39 asa separator or a filter.
 46. An electrolyte battery, energy storagedevice, article, cartridge, or module comprising the membrane of claim21 as a separator or a filter.
 47. An electrolyte battery, energystorage device, article, cartridge, or module comprising the membrane ofclaim 19 as a separator or a filter.
 48. An electrolyte battery, energystorage device, article, cartridge, or module comprising the membrane ofclaim 17 as a separator or a filter.
 49. An electrolyte battery, energystorage device, article, cartridge, or module comprising the membrane ofclaim 15 as a separator or a filter.
 50. An electrolyte battery, energystorage device, article, cartridge, or module comprising the membrane ofclaim 10 as a separator or a filter.
 51. An electrolyte battery, energystorage device, article, cartridge, or module comprising the membrane ofclaim 6 as a separator or a filter.
 52. An article, cartridge, module,battery, energy storage device, packaging, or printing materialcomprising the membrane of claim 1.